US20080067075A1 - Process for plating plastic part after overmolding - Google Patents
Process for plating plastic part after overmolding Download PDFInfo
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- US20080067075A1 US20080067075A1 US11/524,124 US52412406A US2008067075A1 US 20080067075 A1 US20080067075 A1 US 20080067075A1 US 52412406 A US52412406 A US 52412406A US 2008067075 A1 US2008067075 A1 US 2008067075A1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1641—Organic substrates, e.g. resin, plastic
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/285—Sensitising or activating with tin based compound or composition
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/02—Electroplating of selected surface areas
- C25D5/022—Electroplating of selected surface areas using masking means
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
- C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
Definitions
- This invention concerns a process for forming a plastic part, such as a case for a tape measure or other item in which there is a low-durometer grip portion and with other, rigid surfaces of the plastic substrate being plated with a shiny metallic coating.
- the invention is directed to a process in which the rigid plastic part is first subjected to an overmolding step to add the grip portion(s), and is then subjected to a plating or metallizing process.
- This process of overmolding first and then metallizing represents a significant improvement over the conventional technique of metallizing first and then overmolding, as it avoids scratching and damage to the shiny metal surfaces that can occur in the overmolding step.
- Metal plating of plastic materials is commonly done in the industry to provide a decorative, shiny metal finish to a molded plastic part. This can be done using an electroless plating technique or a combination of electroless plating and electroplating.
- a process for metal plating of plastic parts is described in Frankel et al. U.S. Pat. No. 4,803,097.
- Another process for applying a decorative chrome electroplate onto a rigid plastic substrate is described in Donovan, III et al. U.S. Pat. No. 6,468,672. These processes involve plating baths of very low pH (acidic) and with elevated temperatures.
- a process for forming an overmolded grip on a rigid plastic substrate is described in Ajbani et al. Pat. Appln. Pub. No. US 2004/0151933.
- a rubbery polymer is applied onto a plastic part of any of various types, e.g., toothbrush handles, razor handles, hair brushes, pens, kitchen appliances and utensils.
- the polymer can also be applied as a grip portion onto a tool such as a knife or saw handle, or the case or housing of a tape rule.
- the overmolding process involves placing the previously molded rigid plastic substrate into an injection or compression mold where the rubbery polymer is applied over some portions of the substrate.
- the action of placing the previously plated plastic part into the mold does often result in scratching or damaging to the other surfaces, including surfaces that are left uncovered by the overmolded grip portions. These scratches are deemed unacceptable in the finished product, and so the parts or cases with scratching are scrapped.
- the grips are often formed as separate plastic parts, and attached to the plated rigid plastic part.
- This has been one preferred technique in applying rubber-like grip portions to chrome-plated plastic tape rule cases, and this technique is described in Wertheim U.S. Pat. No. 5,746,004 and in Blackman et al. Pat. Appln. Pub. Nos. US 2003/0233762 and US 2005/0028397.
- this technique increases manufacturing costs.
- a molded plastic part is produced that is at least partly metal-plated and which is overmolded with a thermoplastic elastomer that form grip portions.
- a shell or substrate is molded of a rigid polymer.
- the substrate is overmolded, with a thermoplastic elastomer (or TPE) on some portions of the molded substrate, leaving exposed portions of the molded substrate.
- a decorative metal plating is applied onto the exposed portions, but not onto the TPE overmolded grip portions.
- the thermoplastic elastomer is a compound having saturated elastomer midblocks and which is adapted to withstand exposure to the acid environment and elevated temperature of a plating bath.
- the decorative metal plating is carried out by preparing the exposed portions of the molded and overmolded substrate in a bath of chromic acid to etch the surface of said exposed portions. Then the substrate is subjected to electroless palladiumizing in a bath of stannous chloride and palladium chloride to produce a palladium tin layer on the surface of the exposed portions. A subsequent bath removes any plastic residue from the palladium tin layer on the exposed portions. Then the part is placed in successive plating baths of copper, nickel, and chrome for electroplating the palladium tin on the exposed portions, and produces a durable, shiny metal surface.
- thermoplastic elastomer or TPE is a material having a shore hardness between about 40 and 90, although this is not critical.
- the material may have a tensile strength of substantially 60 Kg/cm 2 .
- An acceptable type of thermoplastic elastomer is Empilon (a trademark of Ho Tai Industrial Company, Ltd, of Taipei, Taiwan) of grade PHA 61B.
- Other types of TPE could be employed, depending on the product.
- the step of palladiumizing should be preceded by neutralizing in a bath to remove from the surface of the exposed portions of the substrate hexavalent chrome that results from the etching step.
- the steps of palladiumizing and removing plastic residue should be followed by dipping the substrate in a bath containing nickel sulphate, ammonium chloride, sodium hypophosphite and sodium citrate.
- the sole Drawing FIGURE is a perspective views of the case or housing for a tape measure rule or tape measure, formed by a process according to a preferred embodiment of this invention.
- the FIGURE shows an example of a plastic molded item, namely a case 10 for a tape rule, which is formed of a rigid plastic material, e.g., ABS or polystyrene or polycarbonate, with overmolded grip portions 12 formed of a suitable TPE, which in this embodiment is Empilon PHA 61B.
- the case is fabricated as left and right halves, i.e., a cover half and a hub half, and each of these is subjected to metallization of exposed surfaces 14 , i.e., those not occupied by the grip portions 12 .
- the tape rule case is but one example, and the technique can be used for many other tools and implements or other products where a rubbery grip may be desired.
- the rigid plastic right and left halves of the case are first formed by a traditional plastic molding technique.
- the case substrate is molded of ABS.
- each housing half is provided with the overmolded grip portions, applying the Empilon TPE material.
- one possible TPE has the following characteristics, namely, a specific gravity of 0.91, a Shore (A) durometer hardness of about 40 to 90, a tensile strength of about 60 Kg/cm2, an elongation (at break) of 500%, a melt index of 2 grams per 10 minutes at 200° C. for a 5 Kg test sample, and an adhesive strength with ABS of 6 Kgf/2.5 cm.
- the TPE is black, but if desired could be of another color.
- This TPE can favorably be an SEBS polymer, with styrene end blocks and polybutadiene and butylene mid blocks or center blocks.
- the Shore hardness can be higher or lower than the range mentioned above, depending on the article.
- This particular compound has high weather and oxidation resistance, high processing stability, and normal processing stability at temperatures up to at least 190° C. and up to 260° C.
- the overmolded ABS substrate is placed onto a hanging rack, and is prepared for processing in a number of successive chemical baths, where the metallization is accomplished on the exposed surfaces 14 .
- the substrate or part is first degreased to clean it of grease, dirt, fingerprints and the like, using a standard degreasing compound in aqueous solution at about 50-60° C. for several minutes. This is followed by a water rinse. Then the part is placed into a sulfuric acid solution with a wetting solvent, to enhance the hydrophilic behavior of the exposed ABS surfaces 14 . After this the part is dipped into an etching bath of chromic acid and sulfuric acid at about 65 to 75° C. for a sufficient time (in one example, 8-15 minutes) to etch the surface lightly. After a brief water rinse, the part is neutralized in a bath of CP hydrochloric acid for about a minute to a few minutes. This removes any hexavalent chrome from the etched surface to prepare for the subsequent steps. This is followed by a water rinse.
- the part is next dipped into a bath containing hydrochloric acid, stannous chloride, and palladium chloride in aqueous solution, at ambient (room temperature) for about 90 to 180 seconds (this time is not critical, and can be varied). This is followed by a water rinse. This produces a layer of stannous palladium, i.e., palladium tin, which is chemisorbed onto the exposed ABS surfaces 14 . Then the part is peptized by dipping it into hydrochloric acid at 45 to 60° C. for 90 to 180 seconds (again, this time range is not critical, and depends on the product being plated). This removes plastic residue from the palladium tin. A water rinse follows this step.
- the part is subjected to a number of plating steps for plating successively in copper, nickel and chrome.
- the part is dipped into a nickel plating bath of nickel sulphate, ammonium chloride, sodium hypophosphite and sodium citrate in aqueous solution at 30 to 40° C. for about several minutes (e.g., 5 to 10 minutes) to form a base layer of electroplated nickel.
- a water rinse the part is placed in a copper pre-dip bath of copper pyrophosphate and phosphoric tetrasodium at about 45 to 55° C. for several minutes to enhance the conductivity of the nickel base layer. Then there is another water rinse.
- Copper plating is carried out in a bath of copper sulphate with sulfuric acid for about a sufficient time to create a shiny surface for the part, and in one possible example this is for about 8 to 15 minutes, with current applied at about 2 to 4 amps/dm 2 .
- the part is placed in an activation bath of sulfuric acid for a short time, e.g., 30 to 90 seconds, to remove oxidation from the metal surface.
- the part is placed into a nickel semi-dipping bath, of nickel sulphate, ammonium chloride, and boric acid, at a temperature of about 50 to 60° C., a pH of about 4.0 to 4.6, for a sufficient time, e.g., 4 to 6 minutes at a current density of 2 to 8 amps/dm 2 .
- a sufficient time e.g. 4 to 6 minutes at a current density of 2 to 8 amps/dm 2 .
- the part undergoes a second nickel dipping under the same conditions and this produces a shiny surface on the part.
- the part is dipped into a chrome plating bath of chromic acid and sulfuric acid at about 35 to 43° C. for a few minutes, e.g., 3 to 4 minutes at 10 to 30 amps/dm 2 to give the metallization an anti-wear and anti-corrosive property.
- the solutions used may have concentrations as follows: Degreasing, 7% ⁇ 1%; Etching, 46% ⁇ 2%; Neutralization, 5% ⁇ 1%; Palladiumizing, 9 ⁇ 2 g/L; Peptizing, 2 to 6 g/L; Initial Nickel dipping, 4 ⁇ 0.5 g/L; Copper pre-dipping, 21 ⁇ 2 g/L. In the remaining metal plating, for Copper dipping, 22 ⁇ 2 g/L; Nickel semi-dipping, 20 ⁇ 2 g/L; Nickel dipping 25 to 30 g/L; and Chrome dipping, 20 ⁇ 2 g/L. The skilled process engineer can adjust these as need be to achieve optimal results in any given application.
- the post-overmolding plating as described above does not adversely affect the overmolded TPE grip portions.
- the incidence of scratching or damage to the plated or metallized surfaces is greatly reduced as compared with the more traditional approach of first plating and then overmolding.
Abstract
A plastic part is provided with decorative metallized surfaces as well as overmolded thermoplasticelastomer grip portions. The plastic part is overmolded with the TPE prior to metallizing the remaining exposed surfaces of the part. A TPE compound with saturated midblocks is used which is stable in the acid environment and elevated temperatures of the plating.
Description
- This invention concerns a process for forming a plastic part, such as a case for a tape measure or other item in which there is a low-durometer grip portion and with other, rigid surfaces of the plastic substrate being plated with a shiny metallic coating. In particular, the invention is directed to a process in which the rigid plastic part is first subjected to an overmolding step to add the grip portion(s), and is then subjected to a plating or metallizing process. This process of overmolding first and then metallizing represents a significant improvement over the conventional technique of metallizing first and then overmolding, as it avoids scratching and damage to the shiny metal surfaces that can occur in the overmolding step.
- Metal plating of plastic materials is commonly done in the industry to provide a decorative, shiny metal finish to a molded plastic part. This can be done using an electroless plating technique or a combination of electroless plating and electroplating. A process for metal plating of plastic parts is described in Frankel et al. U.S. Pat. No. 4,803,097. Another process for applying a decorative chrome electroplate onto a rigid plastic substrate is described in Donovan, III et al. U.S. Pat. No. 6,468,672. These processes involve plating baths of very low pH (acidic) and with elevated temperatures.
- A process for forming an overmolded grip on a rigid plastic substrate is described in Ajbani et al. Pat. Appln. Pub. No. US 2004/0151933. A rubbery polymer is applied onto a plastic part of any of various types, e.g., toothbrush handles, razor handles, hair brushes, pens, kitchen appliances and utensils. The polymer can also be applied as a grip portion onto a tool such as a knife or saw handle, or the case or housing of a tape rule. The overmolding process involves placing the previously molded rigid plastic substrate into an injection or compression mold where the rubbery polymer is applied over some portions of the substrate. Where the overmolding process is used for forming grip portions on a metal-plated plastic part, the action of placing the previously plated plastic part into the mold does often result in scratching or damaging to the other surfaces, including surfaces that are left uncovered by the overmolded grip portions. These scratches are deemed unacceptable in the finished product, and so the parts or cases with scratching are scrapped.
- For this reason, the grips are often formed as separate plastic parts, and attached to the plated rigid plastic part. This has been one preferred technique in applying rubber-like grip portions to chrome-plated plastic tape rule cases, and this technique is described in Wertheim U.S. Pat. No. 5,746,004 and in Blackman et al. Pat. Appln. Pub. Nos. US 2003/0233762 and US 2005/0028397. However, because of the additional manufacturing steps involved in attaching the elastomeric grips, this technique increases manufacturing costs.
- It has been desired to provide an effective, efficient, and inexpensive technique for overmolding rubberlike grips onto metal plated plastic parts, such as tape measure cases, and at the same time to avoid the high scrap rates that seem to be inherent in the current technique. However, that objective has thus far eluded the industry.
- Accordingly, it is an object of the present invention to provide a technique for forming metallized rigid plastic parts with overmolded grip portions, and which avoids the drawbacks inherent with the techniques of the prior art.
- It is a more specific object to provide an overmolding technique in which the rigid plastic substrate or shell is first provided with an overmolded grip portion or portions of a suitable TPE polymer, and is thereafter subjected to plating of the remaining exposed surfaces.
- It is a particular objective to provide an overmolding technique which employs materials and techniques that permit the overmolding to occur prior to the metallization.
- In accordance with an aspect of this invention, a molded plastic part is produced that is at least partly metal-plated and which is overmolded with a thermoplastic elastomer that form grip portions. First, a shell or substrate is molded of a rigid polymer. Then the substrate is overmolded, with a thermoplastic elastomer (or TPE) on some portions of the molded substrate, leaving exposed portions of the molded substrate. After this, a decorative metal plating is applied onto the exposed portions, but not onto the TPE overmolded grip portions.
- In a preferred embodiment, the thermoplastic elastomer is a compound having saturated elastomer midblocks and which is adapted to withstand exposure to the acid environment and elevated temperature of a plating bath. The decorative metal plating is carried out by preparing the exposed portions of the molded and overmolded substrate in a bath of chromic acid to etch the surface of said exposed portions. Then the substrate is subjected to electroless palladiumizing in a bath of stannous chloride and palladium chloride to produce a palladium tin layer on the surface of the exposed portions. A subsequent bath removes any plastic residue from the palladium tin layer on the exposed portions. Then the part is placed in successive plating baths of copper, nickel, and chrome for electroplating the palladium tin on the exposed portions, and produces a durable, shiny metal surface.
- Favorably, the thermoplastic elastomer or TPE is a material having a shore hardness between about 40 and 90, although this is not critical. The material may have a tensile strength of substantially 60 Kg/cm2. One example of an acceptable type of thermoplastic elastomer is Empilon (a trademark of Ho Tai Industrial Company, Ltd, of Taipei, Taiwan) of grade PHA 61B. Other types of TPE could be employed, depending on the product.
- The step of palladiumizing should be preceded by neutralizing in a bath to remove from the surface of the exposed portions of the substrate hexavalent chrome that results from the etching step. The steps of palladiumizing and removing plastic residue should be followed by dipping the substrate in a bath containing nickel sulphate, ammonium chloride, sodium hypophosphite and sodium citrate.
- The above and many other objects, features, and advantages of this invention will be more fully appreciated from the ensuing description of selected preferred embodiments, with the description to be read in conjunction with the accompanying Drawing.
- The sole Drawing FIGURE is a perspective views of the case or housing for a tape measure rule or tape measure, formed by a process according to a preferred embodiment of this invention.
- The FIGURE shows an example of a plastic molded item, namely a
case 10 for a tape rule, which is formed of a rigid plastic material, e.g., ABS or polystyrene or polycarbonate, with overmoldedgrip portions 12 formed of a suitable TPE, which in this embodiment is Empilon PHA 61B. Here the case is fabricated as left and right halves, i.e., a cover half and a hub half, and each of these is subjected to metallization of exposedsurfaces 14, i.e., those not occupied by thegrip portions 12. - As discussed before, the tape rule case is but one example, and the technique can be used for many other tools and implements or other products where a rubbery grip may be desired.
- The rigid plastic right and left halves of the case are first formed by a traditional plastic molding technique. In one example, the case substrate is molded of ABS. Then each housing half is provided with the overmolded grip portions, applying the Empilon TPE material. Favorably, one possible TPE has the following characteristics, namely, a specific gravity of 0.91, a Shore (A) durometer hardness of about 40 to 90, a tensile strength of about 60 Kg/cm2, an elongation (at break) of 500%, a melt index of 2 grams per 10 minutes at 200° C. for a 5 Kg test sample, and an adhesive strength with ABS of 6 Kgf/2.5 cm. In this example, the TPE is black, but if desired could be of another color. This TPE can favorably be an SEBS polymer, with styrene end blocks and polybutadiene and butylene mid blocks or center blocks. The Shore hardness can be higher or lower than the range mentioned above, depending on the article. This particular compound has high weather and oxidation resistance, high processing stability, and normal processing stability at temperatures up to at least 190° C. and up to 260° C.
- After the
overmolded grip portions 12 have been added, the overmolded ABS substrate is placed onto a hanging rack, and is prepared for processing in a number of successive chemical baths, where the metallization is accomplished on the exposed surfaces 14. - The substrate or part is first degreased to clean it of grease, dirt, fingerprints and the like, using a standard degreasing compound in aqueous solution at about 50-60° C. for several minutes. This is followed by a water rinse. Then the part is placed into a sulfuric acid solution with a wetting solvent, to enhance the hydrophilic behavior of the exposed ABS surfaces 14. After this the part is dipped into an etching bath of chromic acid and sulfuric acid at about 65 to 75° C. for a sufficient time (in one example, 8-15 minutes) to etch the surface lightly. After a brief water rinse, the part is neutralized in a bath of CP hydrochloric acid for about a minute to a few minutes. This removes any hexavalent chrome from the etched surface to prepare for the subsequent steps. This is followed by a water rinse.
- The part is next dipped into a bath containing hydrochloric acid, stannous chloride, and palladium chloride in aqueous solution, at ambient (room temperature) for about 90 to 180 seconds (this time is not critical, and can be varied). This is followed by a water rinse. This produces a layer of stannous palladium, i.e., palladium tin, which is chemisorbed onto the exposed ABS surfaces 14. Then the part is peptized by dipping it into hydrochloric acid at 45 to 60° C. for 90 to 180 seconds (again, this time range is not critical, and depends on the product being plated). This removes plastic residue from the palladium tin. A water rinse follows this step.
- After this, the part is subjected to a number of plating steps for plating successively in copper, nickel and chrome.
- The part is dipped into a nickel plating bath of nickel sulphate, ammonium chloride, sodium hypophosphite and sodium citrate in aqueous solution at 30 to 40° C. for about several minutes (e.g., 5 to 10 minutes) to form a base layer of electroplated nickel. After a water rinse, the part is placed in a copper pre-dip bath of copper pyrophosphate and phosphoric tetrasodium at about 45 to 55° C. for several minutes to enhance the conductivity of the nickel base layer. Then there is another water rinse.
- Copper plating is carried out in a bath of copper sulphate with sulfuric acid for about a sufficient time to create a shiny surface for the part, and in one possible example this is for about 8 to 15 minutes, with current applied at about 2 to 4 amps/dm2. After water rinsing, the part is placed in an activation bath of sulfuric acid for a short time, e.g., 30 to 90 seconds, to remove oxidation from the metal surface. Then there is a water rinse, and the part is placed into a nickel semi-dipping bath, of nickel sulphate, ammonium chloride, and boric acid, at a temperature of about 50 to 60° C., a pH of about 4.0 to 4.6, for a sufficient time, e.g., 4 to 6 minutes at a current density of 2 to 8 amps/dm2. This enhances the anti-corrosive properties of the metallization. Then the part undergoes a second nickel dipping under the same conditions and this produces a shiny surface on the part. After a water rinse, the part is dipped into a chrome plating bath of chromic acid and sulfuric acid at about 35 to 43° C. for a few minutes, e.g., 3 to 4 minutes at 10 to 30 amps/dm2 to give the metallization an anti-wear and anti-corrosive property.
- In one example, the solutions used may have concentrations as follows: Degreasing, 7%±1%; Etching, 46%±2%; Neutralization, 5%±1%; Palladiumizing, 9±2 g/L; Peptizing, 2 to 6 g/L; Initial Nickel dipping, 4±0.5 g/L; Copper pre-dipping, 21±2 g/L. In the remaining metal plating, for Copper dipping, 22±2 g/L; Nickel semi-dipping, 20±2 g/L; Nickel dipping 25 to 30 g/L; and Chrome dipping, 20±2 g/L. The skilled process engineer can adjust these as need be to achieve optimal results in any given application.
- The post-overmolding plating as described above does not adversely affect the overmolded TPE grip portions. The incidence of scratching or damage to the plated or metallized surfaces is greatly reduced as compared with the more traditional approach of first plating and then overmolding.
- While the invention has been described with reference to a specific preferred embodiment, the invention is certainly not limited to that precise embodiment. Rather, many modifications and variations will become apparent to persons of skill in the art without departure from the scope and spirit of this invention, as defined in the appended claims.
Claims (6)
1. Process for forming a molded plastic part that is at least partly metal plated and which is overmolded with a thermoplastic elastomer to form grip portions, comprising
molding a substrate of a rigid polymer;
overmolding portions of the molded substrate with a thermoplastic elastomer leaving exposed portions of said molded substrate; and thereafter
forming a decorative metal plating on said exposed portions but not on the thermoplastic overmolded grip portions;
wherein said thermoplastic elastomer is a compound having saturated elastomer midblocks and which is adapted to withstand exposure to an acid environment and elevated temperature of a plating bath; and
wherein said forming of the decorative metal plating is carried out by
preparing the exposed portions of the molded and overmolded substrate in a bath of chromic acid to etch the surface of said exposed portions;
electrolessly palladiumizing said substrate in a bath of stannous chloride and palladium chloride to produce a palladium tin layer on the surface of said exposed portions;
removing any plastic residue from the palladium tin layer on said exposed portions; and
electroplating the palladium tin on the exposed portions of the substrate in successive plating baths of copper, nickel, and chrome.
2. The process according to claim 1 wherein said thermoplastic elastomer is a material having a shore hardness between 40 and 90, and a tensile strength of substantially 60 Kg/cm2.
3. The process according to claim 2 wherein said thermoplastic elastomer is an SEBS polymer, with styrene end blocks and polybutadiene and butylene mid blocks.
4. The process according to claim 3 , wherein said thermoplatic elastomer includes is Empilon, PHA 61B.
5. The process according to claim 1 wherein said step of palladiumizing is preceded by neutralizing in a bath to remove hexavalent chrome from the surface of the exposed portions of the substrate.
6. The process according to claim 1 wherein said steps of palladiumizing and removing plastic residue are followed by dipping the substrate in a bath containing nickel sulphate, ammonium chloride, sodium hypophosphite and sodium citrate.
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US11/524,124 US20080067075A1 (en) | 2006-09-20 | 2006-09-20 | Process for plating plastic part after overmolding |
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US11/524,124 US20080067075A1 (en) | 2006-09-20 | 2006-09-20 | Process for plating plastic part after overmolding |
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US20080067075A1 true US20080067075A1 (en) | 2008-03-20 |
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EP2177843A1 (en) * | 2008-10-17 | 2010-04-21 | Dr. Schneider Kunststoffwerke GmbH | Pivotable lamella in a lamella assembly in the casing of an air jet |
US8584373B2 (en) | 2011-09-21 | 2013-11-19 | Stanley Black & Decker, Inc. | Tape rule blade with variable thickness coating |
US8793890B2 (en) | 2011-04-13 | 2014-08-05 | Stanley Black & Decker, Inc. | Tape rule housing |
US20150158256A1 (en) * | 2013-12-11 | 2015-06-11 | Hyundai Motor Company | Method of manufacturing dial knob for opening/closing air vent |
US10766131B2 (en) | 2018-08-01 | 2020-09-08 | Alexander Deiser | Palmar grip |
WO2021015731A1 (en) * | 2019-07-22 | 2021-01-28 | Alexander Deiser | Palmar grip |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2177843A1 (en) * | 2008-10-17 | 2010-04-21 | Dr. Schneider Kunststoffwerke GmbH | Pivotable lamella in a lamella assembly in the casing of an air jet |
US8793890B2 (en) | 2011-04-13 | 2014-08-05 | Stanley Black & Decker, Inc. | Tape rule housing |
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CN104715949A (en) * | 2013-12-11 | 2015-06-17 | 现代自动车株式会社 | Method of manufacturing dial knob for opening/closing air vent |
CN104715949B (en) * | 2013-12-11 | 2018-12-21 | 现代自动车株式会社 | The method that manufacture was used to open/closed the turntable knob of ventilation hole |
US10766131B2 (en) | 2018-08-01 | 2020-09-08 | Alexander Deiser | Palmar grip |
WO2021015731A1 (en) * | 2019-07-22 | 2021-01-28 | Alexander Deiser | Palmar grip |
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