CN1527892A - Method for producing plated molded product - Google Patents
Method for producing plated molded product Download PDFInfo
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- CN1527892A CN1527892A CNA028068580A CN02806858A CN1527892A CN 1527892 A CN1527892 A CN 1527892A CN A028068580 A CNA028068580 A CN A028068580A CN 02806858 A CN02806858 A CN 02806858A CN 1527892 A CN1527892 A CN 1527892A
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- plating
- moulded parts
- coating
- molded product
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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
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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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
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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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth 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
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemically Coating (AREA)
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
Invention field
The present invention relates to make the method for the plated molded product with thin layer, the present invention also relates to the electro-plating method on common injection-molded product surface, this product is the resene mo(u)lded item, and its back side is elastic layer.The present invention be more particularly directed to electrical part or electron device (as switch and manipulation personal electric computer key face), the method for electroplating surface of business automation equipment (as personal electric computer and phone) and Communication Equipment (as DVD and MD), the method for particularly producing mobile phone button (key)
Background of invention
For example, present people more and more require to reduce the thickness of collapsible (slim) mobile phone.For this class mobile phone, its action button (key) must be thin as far as possible.
Usually, action button is that ABS resin (multipolymer of acrylonitrile-butadiene-styrene (ABS)) is injection molded, easily electroplates.Yet, ABS resin and handset bond properties extreme difference, and, consider that for decorating some can not electroplate action button.Can adopt other resin except that ABS resin in this case, as PC (poly-carbon ester) resin.And, can also provide the action button of glossy surface and matt surface (slight uneven surface) for decorative purpose.
Usually, the mobile phone button adopts internal mold method (inmolding) production, and this button does not have match volume, does not have bright effect yet.For avoiding these, by the above, the molded article surface after the injection moulding must be through electroplating altogether.
When producing slim injecting products altogether, adopt the matched molds injection moulding different usually with ordinary method.
And when adopting common injection molding to produce slim moulded parts, resin injects in the former at a high speed usually.If injection molding speed is slow excessively, resin does not advance former, thereby can not get slim moulded parts.Yet if it is too fast to annotate speed, the problem that can cause coating easily to peel off from moulded parts, the reason of consideration are that the mo(u)lded item surface lacks the fixedly ability of coating, and it is by resin flow in the injection molded process or directional property decision.
Especially according to conventional electrochemical plating, adopt electroless plating to form metal plating, adopt electrochemical plating to form nickel dam again on the chemical plating surface in molded article surface; Be plated to chromium or chromium alloy layer in the nickel dam surface electrical again.A kind of like this coating is easy to peel off in tests such as cross cut adhesion test, thermal shocking.
Therefore, the someone forms copper coating by electrochemical plating after considering to adopt electroless plating to form metal plating.Usually copper coating has and all plates effect by force, can cause following point.
In common plating, if the action button surface has slightly crude (as polishing), this crude by coating leveling, produces bright layer, crude disappearance.It is destroyed that promptly electricity generates the back (cavity) feature.
The mobile phone operation button possesses elastic layer, is included among the product by injection molding method altogether, for the mo(u)lded item back side provides cushion.Also have, the injection-molded product surface can be electroplated altogether.
This class mo(u)lded item overlay coating is finished by electroless plating usually, comprises several successive operation stepss such as etch, washing, catalysis, promotion, last re-plating.
In the etch stage, mo(u)lded item is immersed in chromic acid and the vitriolic mixing acid, but in etch, elastic layer is easy to be dissolved in this nitration mixture.Molten component of getting off is reunited in the washing stage subsequently etc., and diffusion in operation subsequently, makes outside small-particle cause substandard products attached to the moulded parts coating surface.
For avoiding this class problem, consider to reduce the concentration of chromic acid mixture, make elastic layer not dissolved.Yet, in this case, the adhesion property extreme difference of the coating of molded article surface.
As a kind of replacement method, can consider after moulded parts is electroplated, elastic layer to be bonded to the back side of moulded parts.Yet productive rate has in this case descended.
When moulded parts (as mobile phone one class button) is being electroplated, carry out pre-treatment (a kind of chemical process) to moulded parts, washing, nickel plating, washing, chromium plating, washing, dry again.In this case, contain sexavalent chrome in the chromium plating bath component of employing, and sexavalent chrome ionization, be deposited on article surface through electrophoretic method again, form metallic chromium layer.Although in metallic chromium layer, do not have hexavalent chromium or trivalent chromic ion one class material, consider that this coating has negative impact to people's skin.Still more, after this series products was discarded, the chromium metal corrosion caused chromic reduction, and chromium still remains in the environment, throws into question.
For avoiding the generation of this situation, studied in chromium plating solution and adopted trivalent chromium.Yet research is from the beginning compared with regard to finding the method that adopts sexavalent chrome to generate metal plating with routine, adopts chromic method can not effectively generate the coating of enough corrosion resistances.
And, altogether the mobile phone operation button of injection molding method production will be with the electroplating processes of carrying out of the trivalent chromium coating bath of new introduction, if the plating condition will cause some problems by the standard controlling valu that factory works out, the required index of user can't effectively be controlled, and just needs change standard controlling valu and equipment.
For example, form trickle protuberance on the plated item surface.Reason may be dust enter solution or electroplate in the impurity that produces carried secretly in the coating.And it is too poor to electroplate hiding power, and reason may be the plated item surface irregularity, and under normalized current density, electric current can't circulate.
Summary of the invention
The plated molded product making method content according to the present invention is electroplated on the mo(u)lded item surface with the thin layer that forms by resin high speed injection molding, and electro-plating method comprises the steps:
(a) adopt electroless plating to form metal plating in molded article surface
(b) adopt electrochemical plating, form copper coating on the chemical plating surface
(c) adopt electrochemical plating, form nickel coating on the copper coating surface
(d) adopt electrochemical plating, form chromium or chromium alloy layer on the nickel coating surface
The implication of high speed injection molding high speed is: on this velocity level, the orientation of butadiene molecule has been changed in the ABS resin.And in common injection moulding speed, butadiene molecule is circular arrangement basically, and when speed during more than or equal to predetermined speed, it is ellipticity and arranges.Therefore, common coating very easily peels off from molded article surface.
In a kind of embodiment, press following condition copper facing:
Moulded parts is immersed in the copper sulfate electrolyzer, and concentration of copper sulfate is 70-90g/L, and sulfuric acid concentration is 170-210g/L, and temperature is between 10-30 ℃, and cathode current density is 1-4A/dm
2
In a kind of embodiment, the surface of moulded parts is wet look and uneven surface.
Adopt above-mentioned any method can make the plated molded goods of the present invention.
In a kind of embodiment, described moulded parts is the action button on the mobile phone.
In an embodiment, the metal plating that is formed by electroless plating is nickel dam, copper layer etc.
According to the present invention,, also can obtain having the coating of antistrip performance even for the mo(u)lded item that obtains by the high speed injection molding with thin layer.Even form coating on the face polishing, this coating also can reappear the face of polishing.
Effect of the present invention is as follows:
After the mo(u)lded item surface forms such as metal plating such as nickel dam or copper layers, form copper coating by electroless plating, after this form nickel coating and chromium or Chrome metal powder coating by electrochemical plating on the copper coating surface again on the chemical plating surface.Therefore, for mo(u)lded item with thin layer, metal plating can be firmly attached to (on the mo(u)lded item) on the top layer down, and have antistrip performance.And plating can reappear finish plate and mo(u)lded item is polished face.
Peel off complexity according to following condition measurement mode plastic coating.
Cross cut adhesion test: 1mm * 1mm cross cut.
Thermal shock test: at 85 ℃, 1 hour and-35 ℃, circulation between 1 hour.Requirement is after circulation is more than six times, and coating must keep intact, and conventional coating is impaired after three times.
Make another content of plated molded article process according to the present invention, the inferior molding product surface that obtains on the part surface at least that is positioned at main moulded parts, by Unitarily molded elastic layer is carried out electroplating processes.Treatment process comprises the surface that moulded parts is immersed in etch moulded parts in chromic acid and the vitriolic mixing acid, and the etch condition is as follows:
(a) mixeding liquid temperature is 65-69 ℃;
(b) mixed solution chromic acid concentration is 370-390g/L; And
(c) the mixed solution sulfuric acid concentration is 190-230g/L.
In one embodiment, described method also comprises washing step, catalytic step and promotion step successively after the etch step.Described promotion step comprises following a few step, being about to moulded parts is immersed in the acidic solution, the pH value of described acidic solution is than the more approaching neutrality of pH value of acidic solution in the catalyzer step, make this acidic solution with the activated carbon contact, so that the impurity in the acidic solution is adsorbed, after this carry out the washing of moulded parts again.
In an embodiment, washing step is included in bottom of gullet and prepares a nozzle, blows small bubbles by nozzle, and towards the mo(u)lded item blow bubble.
In an embodiment, elastic layer is made up of Polyurethane Thermoplastic Elastomer.
Plated molded of the present invention can produce by above-mentioned any method.The plating mo(u)lded item is the mobile phone button.
According to the present invention, can comprise resin moulded pieces and integral molded plastic elastomerics, and not have the surperficial enterprising electroplating of the common plastic injection goods of trickle burr in the resin moulded pieces back side.
Effect of the present invention is as follows:
By under best etch condition, carrying out the etch of common injection molding plastic, can carry out the plating on mo(u)lded item surface restraining the elastic layer dissolved as far as possible simultaneously, and the adhesion property excellence.If the etch condition can not be fully satisfied, then the coating adhesion strength will be not enough, cause the coating durability period to shorten.If etch is excessive, then elastic layer disappears moltenly, causes the mo(u)lded item surface property to descend.The result is that substandard products increase.
Another content of plated molded method produced according to the invention, handle through trivalent chromium plating on the surface of the moulded parts that is made by injection molding altogether.
Treatment process comprises the plating step of carrying out under the following conditions:
(a) trivalent chromium concentration is 6-10g/L in the electrolytic solution;
(b) total impurities≤60ppm in the electrolytic solution;
(c) electrolyte temperature is 40-50 ℃;
(d) electrolytic solution pH is 3.2-3.6;
(e) cathode current density is 3-5A/dm
2And
(f) ratio of anode/cathode is 1.5-2: 1.
In an embodiment, the plating condition also comprises:
(g) rectifier: detectability is answered 〉=more than three times of total current intensity;
(h) filtration capacity: whole electrolytic solution per hour passes through strainer more than seven times continuously.
In an embodiment, moulding is a silver color mobile phone operation button.
Make another content of plated molded article process according to the present invention, handle through trivalent chromium plating on the surface of the moulded parts that is made by injection molding altogether.Treatment process comprises the plating step of carrying out under the following conditions:
(a) trivalent chromium concentration is 5-10g/L in the electrolytic solution;
(b) total impurities≤60ppm in the plating bath;
(c) electrolyte temperature is 53-63 ℃;
(d) electrolytic solution pH is 3.2-3.6;
(e) cathode current density is 3-5A/dm
2And
(f) ratio of anode/cathode is 1.5-2: 1.
In an embodiment, the plating condition also comprises:
(g) rectifier: detectability is answered 〉=more than three times of total current intensity;
(h) filtration capacity: whole electrolytic solution per hour passes through strainer more than seven times continuously.
In an embodiment, mo(u)lded item is dark buttons on the mobile phone.
Can make plated molded according to above-mentioned either party's method.
According to the present invention, employing does not contain hexavalent chromium-treatments liquid and carries out surface treatment, can form the chemical transformation coating with excellent anti corrosive power.
Effect of the present invention is as follows:
In the present invention, can change the plating condition according to following items:
(1) surface elevation (with tramp material, slight crack etc.)
Improve the strainability of electrolytic solution, change its Control of Impurities value, finally improved liquid endoparticle uniformity consistency (raising filtering accuracy) and reduced external dirt settling.
(2) hiding power
Adjust the strength of fluid span of control, reset fluid temperature standard and pH value.
Need point out that especially metal concentration is compared with ordinary method and heightened in the electrolytic solution, thereby has improved hiding power.And speed of reaction has improved has also improved hiding power.In addition, improve the pH value and also increased speed of reaction.
Brief Description Of Drawings
Figure 1 shows that the cross sectional representation of the plated molded goods that making method of the present invention obtains.
Figure 2 shows that the cross sectional representation of another plated molded goods that making method of the present invention obtains.
Preferred forms
(first invention)
As shown in Figure 1, according to the present invention, slim mo(u)lded item 14 comprises the slim part 13 that common injection molding forms.And slim mo(u)lded item 14 comprises main mo(u)lded item of being made by ABS resin 11 and the inferior mo(u)lded item 12 that is formed on main mo(u)lded item internal surface by common injection molding.Inferior mo(u)lded item 12 can be by making as PC transparent resins such as (poly-carbon esters).
Thickness≤the 0.35mm of the slim part of discoid moulding 14 is preferably between the 0.15-0.30mm.Mo(u)lded item can adopt common injection molding to make, and wherein former is just in time opposite with formpiston.
Because the existence of slim part, injection moulding speed is faster than ordinary method.
So the mo(u)lded item with slim part that forms follows these steps to electroplate on the mo(u)lded item surface again.
(a) mo(u)lded item adopts chemically coated nickel method or electroless copper method to form metal plating on the mo(u)lded item surface after washing.
Follow these steps to carry out electroless plating
Etch: mo(u)lded item is immersed in the chromic acid and vitriolic mixing aqueous acid under the preset temperature, washing then, molded article surface roughen.
Catalysis: moulded parts is immersed in and contains Palladous chloride, in tin protochloride and the aqueous solution of hydrochloric acid, with after scouring, makes palladium be adsorbed on the moulded piece surface.
Promote: moulded parts is immersed in the aqueous hydrochloric acid, with after scouring, makes that the tin that adsorbs together with palladium in the catalytic process is molten to get off, and enters hydrochloric acid soln.
Chemical nickel plating or electroless copper:
Moulded parts is immersed in the mixed solutions such as nickel or copper, formaldehyde, Rochelle salt, sodium hydroxide, water, sodium hypophosphite, ammoniacal liquor, with after scouring, because the reductive action of formaldehyde and sodium hypophosphite is deposited on the palladium nickel (copper).
Next step is electroplated on the chemical plating surface as follows.
In the present invention, nickel plating and chromium plating or Chrome metal powder again after the copper facing.
(b) adopt electrochemical plating to form copper coating on the chemical plating surface
The thickness of copper coating is usually between 5-15 μ m.
The condition of copper coating is as follows:
Mo(u)lded item is immersed in the electrolytic solution of sulfur acid copper, and the concentration of copper sulfate is 70-90g/L, and sulfuric acid concentration is 170-210g/L, and temperature is 10-30 ℃ (being preferably in 20 ℃), with cathode current density 1-4A/dm
2Electroplate.
The present invention adopts non-all copper sulfate of plating (non-leveling).Because copper sulfate has excellence plating property (followingness) again, so the bump of the part formation sand blasting pattern of the original surface of moulded parts process sandblasting, and flat (wet look) presents brightness effect that its obtains usually.
(c) adopt electrochemical plating to form nickel dam on the copper coating surface.
Layered product is immersed in the mixed solution of single nickel salt, nickelous chloride, boric acid and brightener, handles under predetermined voltage and current condition, with after scouring, forms nickel coating in molded article surface.
(d) adopt electrochemical plating to form chromium and chromium alloy layer on the nickel coating surface.
After this, layered product is through the washing after drying.
In this mode, layered product comprises different resins material part (15,16).Therefore, molded article surface can be transparent.Perhaps, scrape off molded article surface part coating, firmly mo(u)lded item is attached to caking agent on the silicone rubber plate of handset.
As mentioned above, common copper sulfate has extremely strong covering power.Therefore, the smooth part (wet look) of sandblast part (uneven surface) and bottoming is all caused wet look by plating.
On the contrary, the non-copper sulfate that all plates is electroplated and to be had excellence plating property (followingness) again according to the present invention.Therefore, coating can be kept the protuberance of the sandblast part (uneven surface) of bottom, and the smooth part of bottom (wet look) causes brightness effect usually.
(second invention)
Figure 2 shows that mo(u)lded item 24 of the present invention,, make by being total to injection molding as the mobile phone operation button.Mo(u)lded item 24 comprises main mo(u)lded item 21 that the resin injection molding forms and forms by injection molding altogether at the main mo(u)lded item back side, makes the elastic layer 22 of time moulding compound.
Main mo(u)lded item 21 is by ABS resin, polypropylene, vinyl chloride resin, polystyrene, poly-carbon ester, methacrylic resin, polysulfones, polyester, polyacetals, polymeric amide etc., preferred especially ABS resin.
Inferior mo(u)lded item (elastic layer) 22 is made up of rubber, elastomerics etc.22 one-tenth of this elastic layers the cushion of action button.The Shore hardness of elastic layer 22 is preferably between the 85-92 greater than 80.22 one-tenth of elastic layers the cushion of button, improved the operability of button.In case fall on the ground as mobile phone one quasi-instrument, it can play cushioning effect, avoid damage.
The surface of the mo(u)lded item 24 that obtains thus forms coating 23 through following electroplating processes.
(A) clean moulded parts, nickel electroless plating or copper electroless plating are carried out in its surface, form metal plating.Carry out electroless plating as follows.
A-1. etch
Moulded parts is immersed in chromic anhydride and the vitriolic mixed solution, handles in the time at preset temperature, with after scouring, makes the molded article surface roughen.
In this step, treatment condition are preferably as follows:
The temperature of chromic acid mixture is preferably 65-69 ℃, and the best is 66-68 ℃.
Chromic acid concentration is preferably between the 370-390g/L in the chromic acid mixture;
Sulfuric acid concentration is preferably between the 190-230g/L;
The etch treatment time reaches 8-12 minute usually.
If chromic acid concentration too is higher than above-mentioned scope, elastic layer 22 can cause dissolving, and impurity dissolves in mixed solution.If sulfuric acid concentration too is higher than above-mentioned scope, can separate out crystal, restrained the continuity of producing.Reason is that sulfuric acid concentration is too high, causes in the chromic acid mixture chromic acid by saturated.
Before the above-mentioned etch process, carry out the preimpregnation erosion earlier.In this case, pre-etch condition is as follows:
Preimpregnation:
The chromic acid mixture temperature is preferably in 66-68 ℃;
Chromic acid concentration is preferably between the 135-165g/L in the chromic acid mixture;
Sulfuric acid concentration is preferably between the 180-220g/L;
The etch treatment time reaches 2-4 minute usually.
A-2. washing
In order to remove above-mentioned chromic acid mixture from molded article surface, must wash.Use the water wash moulded parts during washing.And, after the washing, must carry out neutralization reaction if necessary, wash with water more subsequently.
A-3. catalysis
Above-mentioned moulded parts is immersed in Palladous chloride, tin protochloride and the hydrochloric acid soln, and with after washing, palladium is attracted to molded article surface.
In the catalytic process, flood in following condition:
Temperature: 31-35 ℃;
Concentration (catalyzer): 53-67g/L;
Concentration (hydrochloric acid): 280-320g/L;
Concentration (impurity chromium) :≤150ppm;
What washing was adopted is drip washing.
A-4. promote
Moulded parts is immersed in the hydrochloric acid soln, with after washing.The tin that is adsorbed together with palladium under katalysis, dissolving, and enter hydrochloric acid soln.
Best submerged conditions is as follows in the promotor step:
Temperature: 36-40 ℃;
Impurity (tin) :≤100ppm.
In this step, if mo(u)lded item directly washes with water, then the pH value of the acidic solution in the catalytic step (pH=1 usually) improves rapidly, produces oxyhydroxide one class impurity, might be attached to the mo(u)lded item surface.For avoiding this situation, the pH value of acidic solution is 1.5, and allows this acidic solution by activated carbon, absorption impurity.
In washing step, adorn a mouth that can blow small bubbles at bottom of gullet, be used for washing elastomerics 22.Bubble impacts molded article surface (particularly elastomerics 22), thereby removes impurity and residual reagent attached to molded article surface effectively.
A-5. chemical Ni-plating layer or copper layer
Moulded parts is immersed in the mixed solutions such as nickel or copper, formaldehyde, Rochelle salt, sodium hydroxide, water, sodium hypophosphite, ammoniacal liquor, with after scouring.Because the reductive action of formaldehyde and sodium hypophosphite, nickel (copper) is deposited on the palladium.
After this, by the following step at the enterprising electroplating of chemical plating.
Among the present invention, carry out the plating of nickel, chromium, Chrome metal powder, gold or other alloy after chemical nickel plating or the electroless copper.
(the 3rd invention)
By the following step, carry out trivalent chromium plating on above-mentioned surface with moulded parts of slim part.
(A) washing moulded parts by chemical nickel plating or electroless copper, forms metal plating in molded article surface.
Carry out electroless plating by the following step:
Etch: moulded parts is immersed in and contains in the chromic anhydride and the vitriolic aqueous solution, carries out electroless plating under the preset temperature, and with after washing, molded article surface becomes coarse.
Catalysis: above-mentioned moulded parts is immersed in Palladous chloride, and in tin protochloride and the hydrochloric acid soln, with after washing, palladium is attracted to molded article surface.
Promote: moulded parts is immersed in the hydrochloric acid soln, with after washing.The tin that is adsorbed together with palladium dissolves under katalysis, and enters hydrochloric acid soln.
Chemical nickel plating or electroless copper:
Moulded parts is immersed in the mixed solutions such as nickel or copper, formaldehyde, Rochelle salt, sodium hydroxide, water, sodium hypophosphite, ammoniacal liquor, and with after scouring, because the reductive action of formaldehyde and sodium hypophosphite, nickel (copper) is deposited on the palladium.
Next step follows these steps to electroplate on chemical plating.
Among the present invention, carry out nickel plating, chromium plating and Chrome metal powder after the copper facing.
(B) adopt electrochemical plating, form copper coating on the chemical plating surface.
The thickness of copper coating is usually between 5-15 μ m.
The copper facing condition is as follows: moulded parts is immersed in the copper sulfate electrolyte, and concentration of copper sulfate is 70-90g/L, sulfuric acid concentration 170-210g/L, and temperature is at 10-30 ℃, cathode current density 1-4A/dm
2
(C) adopt electrochemical plating, form nickel dam on the copper coating surface.
Layered product is immersed in the mixed solution of single nickel salt, nickelous chloride, boric acid and brightener, handles under predetermined voltage and current condition, with after scouring, forms nickel coating in molded article surface.
Wash after the plating, preferably by special device, make the water vibration, thereby infiltrate between the main mo(u)lded item of plastic injection goods altogether and inferior mo(u)lded item 1 and 2 in the gap, liquid just can thoroughly be driven away.
(D) adopt electrochemical plating, form chromium or chromium alloy layer on the nickel coating surface
In the present invention, carry out trivalent chromium plating.For example electroplate liquid is composed as follows:
Chromium sulphate (III), chromium acetate (III), chromium nitrate (III), chromium chloride (III) or phosphoric acid hydrogen chromium (III) are (referring to Japanese publication number, No.2000-54157)
In this example, silver color coating condition is as follows:
A) trivalent chromium concentration: 6-10g/L (preferably 7-9g/L);
B) total impurities in the electrolytic solution :≤60ppm (best≤35ppm);
C) electrolyte temperature: 40-50 ℃ (preferably 47-49 ℃);
D) electrolytic solution pH:3.2-3.6 (preferably 3.35-3.45);
E) cathode current density: 3-5A/dm
2(best 3.5-4.5A/dm
2);
F) ratio of anode/cathode: 1.5-2: 1;
G) rectifier: detectability is answered 〉=more than three times of total current intensity;
H) filtration capacity: whole electrolytic solution per hour passes through strainer more than seven times continuously.Especially, ordinary method circulation of elecrolyte amount is secondary per hour, and internal circulating load of the present invention reaches per hour seven times to ten times.Strainer mesh size is preferably 5-10m (the about 50-100m of ordinary method).And electrolyzer preferably applies electric current above-mentioned all the time.
In order to obtain the black moulded parts, treatment condition only below several respects change
(a ') electrolytic solution trivalent chromium concentration: 6-10g/L (preferably 6-9g/L)
(c ') electrolyte temperature 53-63 ℃ (preferably 57-59 ℃)
(d ') electrolytic solution pH:3.2-3.6 (preferably 3.45-3.55)
Therefore, chrome liquor concentration and electrolyte temperature improve 2%, and it is about 0.2 that pH value descends, and compares the filtration capacity raising more than 2.5 times with the standard plating condition that manufacturer is recommended, thereby might reduce impurity level.
(embodiment 1)
The inferior mo(u)lded item that main mo(u)lded item that ABS resin is made by injection molding altogether and Polyurethane Thermoplastic Elastomer make is moulded the mobile phone push button element altogether.
The etch under following condition of this moulded parts.After the etch, wash with water twice.Each washings is by filtering membrane (2#), detect by an unaided eye be adsorbed on residue on the filter paper (by the poorest be 50 to evaluate its quality to being preferably 0).And washing post moulding goods adopt ordinary method to electroplate, and with the naked eye check the coating of moulded parts.
A. test objective
Can think that Polyurethane Thermoplastic Elastomer has been dissolved in above-mentioned second kind of etch step (second invention in A-1), solidify again after the washing that the elastomerics after the curing is dispersed in subsequently in the operation steps, what produce is substandard products.Reason is that chromic acid or sulfuric acid cause in the chromic acid mixture after being, once through research.
B. test conditions
Chromic acid mixture is made by the chromic acid (350-410g/L, every kind of poor 30g/L) of three kinds of concentration specifications and sulfuric acid (180-240g/L, the every kind of poor 30g/L) combination of three kinds of concentration specifications.
C. test method
The various chromic acid mixtures that prepare are above poured in the 1L beaker.Six above-mentioned moulded partss are immersed in each mixed solution, etch 8 minutes, and corrosion-tank finishing process repeats secondary.
D. the method for inspection
The moulded parts washed twice of etch in the C joint, each washing water flow through filtering membrane (2
#).Detect by an unaided eye be adsorbed on residue on the filter paper (by the poorest be 50 to being preferably 0 its quality of evaluation).Observe attached to the oil film on the filter paper.
E. the results are shown in table 1
Table 1
| Numbering | Etching solution concentration | Washing for the first time | Washing for the second time | The test-results of plated item | |||||||
| Chromic acid | Sulfuric acid | Residue | Oil film | Residue | Oil film | n＝ | ??p＝ | ??％ | The protuberance size | The protuberance area | |
| ??1 | ??410g/l | ?180g/l | ????50 | Have slightly | ????3 | Do not have | 40 | ??23 | ?58 | Greatly | Greatly |
| ??2 | ??380g/l | ?180g/l | ????50 | Many | ????3 | Many | 48 | ??45 | ?94 | Greatly | Greatly |
| ??3 | ??350g/l | ?18Qg/l | ????40 | Many | ????10 | Many | 80 | ??80 | ?100 | Greatly | Greatly |
| ??4 | ??410g/l | ?210g/l | ????20 | Many | ????1 | Have slightly | 48 | ??6 | ?13 | In | In |
| ??5 | ??380g/l | ?210g/l | ????1 | Have slightly | ????2 | Do not have | 40 | ??8 | ?20 | In | Little |
| ??6 | ??350g/l | ?210g/l | ????5 | Many | ????3 | Have slightly | 96 | ??4 | ?4 | In | In |
| ??7 | ??410g/l | ?240g/l | ????2 | Have slightly | ????1 | Have slightly | 48 | ??32 | ?67 | Little | In |
| ??8 | ??380g/l | ?240g/l | ????1 | Do not have | ????1 | Have slightly | 48 | ??27 | ?56 | In | In |
| ??9 | ??350g/l | ?240g/l | ????1 | Do not have | ????1 | Do not have | 48 | ??34 | ?71 | In | In |
In table 1, n represents test number (TN), and p represents substandard products quantity, and % represents fraction defective, and the protuberance size is a visual observation with area.
From table 1 obviously as seen, when chromic acid concentration is 380g/L, when sulfuric acid concentration is 210g/L, the best as a result.When sulfuric acid concentration is in the test of 240g/L, on the beaker liquid level, be formed with liquid crystal, show that this condition is not suitable for actual production, reason is that the too high chromic acid that causes of sulfuric acid concentration is saturated in mixed solution.
(embodiment 2)
The moulded parts of nickel coating carries out trivalent chromium plating under following condition, obtain silver color mobile phone button.
(a) trivalent chromium concentration in the electrolytic solution: 9g/L
(b) electrolytic solution total impurities :≤35ppm
(c) electrolyte temperature: 48 ℃
(d) electrolytic solution pH:3.4
(e) cathode current density: 4.0A/dm
2
(f) ratio of anode/cathode: 1.5: 1
(g) rectifier: detectability is answered 〉=more than three times of total current intensity
(h) filtration capacity: whole electrolytic solution per hour passes through strainer more than seven times continuously.
As a result, silver color mobile phone button has good plating hiding power, no uneven surface.
(embodiment 3)
The moulded parts of nickel coating carries out trivalent chromium plating under following condition, obtain black mobile phone button.
(a) trivalent chromium concentration in the electrolytic solution: 9g/L
(b) electrolytic solution total impurities :≤35ppm
(c) electrolyte temperature: 58 ℃
(d) electrolytic solution pH:3.5
(e) cathode current density: 4.0A/dm
2
(f) ratio of anode/cathode: 1.5: 1
(g) rectifier: detectability is answered 〉=more than three times of total current intensity
(h) filtration capacity: whole electrolytic solution per hour passes through strainer more than seven times continuously.
As a result, black mobile phone button has good plating hiding power, no uneven surface.
(comparative example 1)
The moulded parts of nickel coating carries out trivalent chromium plating under following condition, obtain silver color mobile phone button.
(a) trivalent chromium concentration in the electrolytic solution: 5g/L
(b) electrolytic solution total impurities: 600ppm
(c) electrolyte temperature: 40 ℃
(d) electrolytic solution pH:3.2
(e) cathode current density: 7.0A/dm
2
(f) ratio of anode/cathode: 1.5: 1
(g) rectifier: detectability should 〉=a times of total current intensity
(h) filtration capacity: whole electrolytic solution is per hour continuously by the strainer secondary.
As a result, silver color mobile phone button has good plating hiding power, no uneven surface.
(comparative example 2)
The moulded parts of nickel coating carries out trivalent chromium plating under following condition, obtain black mobile phone button.
(a) trivalent chromium concentration in the electrolytic solution: 8g/L
(b) electrolytic solution total impurities :≤640ppm
(c) electrolyte temperature: 50 ℃
(d) electrolytic solution pH:3.4
(e) cathode current density: 7.0A/dm
2
(f) ratio of anode/cathode: 1.5: 1
(g) rectifier: detectability should 〉=two times of total current intensity
(h) filtration capacity: whole electrolytic solution is per hour continuously by the strainer secondary.
As a result, black mobile phone button has good plating hiding power, no uneven surface.
Differentiate uneven surface by following method: beyond 30cm, foreign matter that eye-observation adheres to and slight crack etc.If the exotic diameter surpasses the product of 0.2mm and is judged to and scraps.
Differentiate by following method and to electroplate hiding power: examine whether uniformity of coating with observing, whether fade, whether tarnish etc.The product that fades, tarnishes is judged to waste product.
Industrial use
According to the first invention, even for the moulding article with slim part that is made by the high speed injection molding, also can obtain the coating of anti-strip. And even form coating at the face of polishing, this coating also can reappear the face of polishing.
According to the second invention, by the etch of molded article surface, the coating that forms at common injection-molded product has good adhesive force, can also avoid the dissolving of elastic layer simultaneously as far as possible. Therefore, might prevent the molded article surface rear formation protuberance that is impacted, thereby reduce scrappage.
According to the 3rd invention, adopt not chromyl treatment fluid to carry out surface treatment, the coat of metal that obtains has excellent corrosion stability. And, to compare with the standard plating condition that production firm is recommended, it is about 2% that chromic acid concentration and electrolyte temperature improve, and it is about 0.2 that pH value reduces, and filter capacity improves more than 2.5 times, so might reduce impurity.
Claims (14)
1. the making method of plated molded product is characterized by: molded article surface has the slim part that resin high speed injection molding forms, and electroplates thereon, and electro-plating method comprises:
(a) adopt electroless plating to form metal plating in molded article surface;
(b) adopt electrochemical plating to form copper coating on the chemical plating surface;
(c) adopt electrochemical plating to form nickel coating on the copper coating surface; And
(d) adopt electrochemical plating to form chromium or Chrome metal powder coating on the nickel coating surface.
2. the method for claim 1 is characterized by: carry out copper facing under following condition:
Moulded parts is immersed in the copper sulfate electrolyte, and concentration of copper sulfate is 70-90g/L, sulfuric acid concentration 170-210g/L, and temperature is at 10-30 ℃, cathode current density 1-4A/dm
2
3. the method for claim 1, it is characterized by: there are wet look and uneven surface in the surface of moulded parts.
4. the plated molded product of making according to the method for claim 1.
5. plated molded product as claimed in claim 4 is characterized by: mo(u)lded item is the mobile phone operation button.
6. the making method of plated molded product is characterized by: molded article surface has the resin slim part that forms of injection molding altogether at a high speed, electroplates thereon.Electro-plating method comprises:
(a) adopt electroless plating to form metal plating in molded article surface;
(b) adopt electrochemical plating to form copper coating on the chemical plating surface;
(c) adopt electrochemical plating to form nickel coating on the copper coating surface; And
(d) adopt electrochemical plating to form chromium or Chrome metal powder coating on the nickel coating surface.
7. the method for plated molded goods is characterized by: the inferior molding product surface that is obtained on the part surface at least that is positioned at main moulded product, by the integral molded plastic elastic layer is carried out electroplating processes.Treatment process comprises the surface that moulded parts is immersed in etch moulded parts in chromic acid and the vitriolic mixing acid, and the etch condition is as follows:
(a) mixeding liquid temperature is 65-69 ℃;
(b) mixed solution chromic acid concentration is 370-390g/L; And
(c) the mixed solution sulfuric acid concentration is 190-230g/L.
8. method as claimed in claim 7 is characterized by: also comprise successively in the operation steps after etch: washing, catalysis and promotion; Wherein,
Promote to comprise moulded parts is immersed in the acidic solution in the step that its pH value is than the more approaching neutrality of pH value of acidic solution in the catalytic step, this acidic solution is adsorbed the impurity in the acidic solution with the activated carbon contact, after this washs moulded parts again.
9. method as claimed in claim 8 is characterized by: washing step is included in bottom of gullet and prepares a nozzle, blows small bubbles by nozzle, and towards the moulded parts blow bubble.
10. method as claimed in claim 7, it is characterized by: elastic layer is made up of thermoplastic elastomer.
11. method as claimed in claim 7 and the plated molded product that makes.
12. plated molded product as claimed in claim 7 is characterized by: mo(u)lded item is the mobile phone operation button.
13. the making method of plated molded goods is characterized by: by being total to the surface that injection molding makes moulded parts, handle through trivalent chromium plating, treatment process comprises following condition:
(a) trivalent chromium concentration is 6-10g/L in the electrolytic solution;
(b) total impurities≤60ppm in the electrolytic solution;
(c) electrolyte temperature is 40-50 ℃;
(d) electrolytic solution pH is 3.2-3.6;
(e) cathode current density is 3-5A/dm
2And
(f) ratio of anode/cathode is 1.5-2: 1.
14. the making method of plated molded goods is characterized by: by being total to the surface that injection molding makes moulded parts, handle through trivalent chromium plating, treatment process comprises following condition:
(a) trivalent chromium concentration is 5-10g/L in the electrolytic solution;
(b) total impurities≤60ppm in the electrolytic solution;
(c) electrolyte temperature is 53-63 ℃;
(d) electrolytic solution pH is 3.2-3.6;
(e) cathode current density is 3-5A/dm
2And
(f) ratio of anode/cathode is 1.5-2: 1.
Applications Claiming Priority (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP041029/2001 | 2001-02-16 | ||
| JP2001041029A JP3685999B2 (en) | 2001-02-16 | 2001-02-16 | Manufacturing method of plated molded products |
| JP041029/01 | 2001-02-16 | ||
| JP192023/2001 | 2001-06-25 | ||
| JP2001192023A JP3722724B2 (en) | 2001-06-25 | 2001-06-25 | Manufacturing method of plated molded products |
| JP192023/01 | 2001-06-25 | ||
| JP322754/01 | 2001-10-19 | ||
| JP322754/2001 | 2001-10-19 | ||
| JP2001322754A JP3710408B2 (en) | 2001-10-19 | 2001-10-19 | Manufacturing method of plated molded products |
| PCT/JP2002/001274 WO2002064862A2 (en) | 2001-02-16 | 2002-02-14 | Method for producing plated molded product |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005101294130A Division CN1804140A (en) | 2001-02-16 | 2002-02-14 | Method for producing mobile phone button |
| CNB2005101294126A Division CN100547120C (en) | 2001-02-16 | 2002-02-14 | The manufacture method of plated molded button of mobile phone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1527892A true CN1527892A (en) | 2004-09-08 |
| CN100360716C CN100360716C (en) | 2008-01-09 |
Family
ID=27346013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028068580A Expired - Fee Related CN100360716C (en) | 2001-02-16 | 2002-02-14 | Method for producing plated molded product |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1360347A2 (en) |
| CN (1) | CN100360716C (en) |
| MY (2) | MY142899A (en) |
| TW (1) | TW554086B (en) |
| WO (1) | WO2002064862A2 (en) |
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| WO2008101413A1 (en) * | 2007-02-15 | 2008-08-28 | Shanghai Amphenol Airwave Communication Electronics Co., Ltd | A method for manufacturing an antenna and an antenna structure |
| CN100431080C (en) * | 2005-04-29 | 2008-11-05 | 乐金电子（昆山）电脑有限公司 | Press button module and its producing method |
| CN101210334B (en) * | 2006-12-29 | 2010-04-21 | 佛山市顺德区汉达精密电子科技有限公司 | Technique for treating plastic surface |
| CN101090596B (en) * | 2006-06-14 | 2011-11-09 | Lg电子株式会社 | Antistatic component |
| CN102216536B (en) * | 2008-09-26 | 2014-05-07 | 科勒公司 | Stainless steel plumbing fixtures with resistant coatings |
| CN104073846A (en) * | 2014-06-25 | 2014-10-01 | 陕西华夏粉末冶金有限责任公司 | Preparation method of copper-nickel alloy sheet part by resin electroplating and atmosphere reduction |
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| JP2004256876A (en) * | 2003-02-26 | 2004-09-16 | Taiyo Manufacturing Co Ltd | Method of producing plated molding |
| JP2004327306A (en) * | 2003-04-25 | 2004-11-18 | Sunarrow Ltd | Multicolored molded resin component for mobile apparatus |
| EP1876268B1 (en) | 2006-06-13 | 2013-05-15 | Wolf-Dieter Franz | Black chromium process free of Cr-VI |
| US20120156443A1 (en) * | 2010-12-15 | 2012-06-21 | David Reeder | Methods of multi-shot injection molding and metal-plated surface coated polymeric articles made therefrom |
| US9062386B2 (en) | 2011-03-01 | 2015-06-23 | Srg Global, Inc. | Methods of multi-shot injection molding and metal-plated polymeric articles made therefrom |
| FR2985741B1 (en) | 2012-01-12 | 2015-05-29 | Albea Services | GOLD OR SILVER METALLIC SILVER PLASTIC PRODUCT FREE OF GOLD AND SILVER ELEMENT AND PROCESS FOR MANUFACTURING SAME. |
| DE102015109506B4 (en) * | 2015-06-15 | 2018-12-20 | Dr. Schneider Kunststoffwerke Gmbh | Method for selective metallization of plastic parts and component |
| CN108683762B (en) * | 2018-05-22 | 2021-07-06 | Oppo广东移动通信有限公司 | Decorative ring, functional assembly, electronic device and processing method of decorative ring |
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| US3655433A (en) * | 1970-07-06 | 1972-04-11 | Standard Oil Co | Platable polymers |
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| EP0102133A3 (en) * | 1982-03-26 | 1985-04-10 | General Electric Company | Metallized article composed of polyphenylene ether resin, high impact polystyrene, alumina and, optionally, a styrene-butadiene radial teleblock copolymer |
| US4395313A (en) * | 1982-07-29 | 1983-07-26 | General Motors Corporation | Vacuum pretreatment process for durable electroplated coatings on ABS and PPO plastics |
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| JPS60155257A (en) * | 1984-09-14 | 1985-08-15 | 住友ノ−ガタツク株式会社 | Plated product |
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-
2002
- 2002-02-07 TW TW091102193A patent/TW554086B/en not_active IP Right Cessation
- 2002-02-14 MY MYPI20020502A patent/MY142899A/en unknown
- 2002-02-14 MY MYPI20080007A patent/MY148983A/en unknown
- 2002-02-14 EP EP02700586A patent/EP1360347A2/en not_active Withdrawn
- 2002-02-14 WO PCT/JP2002/001274 patent/WO2002064862A2/en active Application Filing
- 2002-02-14 CN CNB028068580A patent/CN100360716C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100431080C (en) * | 2005-04-29 | 2008-11-05 | 乐金电子（昆山）电脑有限公司 | Press button module and its producing method |
| CN101090596B (en) * | 2006-06-14 | 2011-11-09 | Lg电子株式会社 | Antistatic component |
| CN101210334B (en) * | 2006-12-29 | 2010-04-21 | 佛山市顺德区汉达精密电子科技有限公司 | Technique for treating plastic surface |
| WO2008101413A1 (en) * | 2007-02-15 | 2008-08-28 | Shanghai Amphenol Airwave Communication Electronics Co., Ltd | A method for manufacturing an antenna and an antenna structure |
| CN102216536B (en) * | 2008-09-26 | 2014-05-07 | 科勒公司 | Stainless steel plumbing fixtures with resistant coatings |
| CN104073846A (en) * | 2014-06-25 | 2014-10-01 | 陕西华夏粉末冶金有限责任公司 | Preparation method of copper-nickel alloy sheet part by resin electroplating and atmosphere reduction |
| CN104626448A (en) * | 2015-01-15 | 2015-05-20 | 温兵 | Manufacturing process of shell |
Also Published As
| Publication number | Publication date |
|---|---|
| MY142899A (en) | 2011-01-31 |
| WO2002064862A3 (en) | 2003-08-28 |
| EP1360347A2 (en) | 2003-11-12 |
| CN100360716C (en) | 2008-01-09 |
| MY148983A (en) | 2013-06-28 |
| WO2002064862A2 (en) | 2002-08-22 |
| TW554086B (en) | 2003-09-21 |
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