CN1530464A - Method for producing molded goods plating - Google Patents

Method for producing molded goods plating Download PDF

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Publication number
CN1530464A
CN1530464A CNA2004100082949A CN200410008294A CN1530464A CN 1530464 A CN1530464 A CN 1530464A CN A2004100082949 A CNA2004100082949 A CN A2004100082949A CN 200410008294 A CN200410008294 A CN 200410008294A CN 1530464 A CN1530464 A CN 1530464A
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CN
China
Prior art keywords
nickel
plating
moulded product
coating
plating bath
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Granted
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CNA2004100082949A
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Chinese (zh)
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CN1297693C (en
Inventor
林一郎
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Taiyo Manufacturing Works Co Ltd
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Taiyo Manufacturing Works Co Ltd
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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
    • 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
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • 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
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • 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
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
    • 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
    • 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
    • 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)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Chemically Coating (AREA)

Abstract

In the method of producing a plated molding, the surface of a molding is subjected to plating by the following stages: a stage (a) where a metal plated layer is formed on the surface of the molding by electroless plating; a stage (b) where a first nickel plated layer is formed on the surface of the electroless plated layer by electroplating; a stage (c) where a second nickel plated layer is formed on the surface of the first nickel plated layer by electroplating; and a stage (d) where a third nickel plated layer is formed on the surface of the second nickel plated layer.

Description

Produce the method for electroplating moulded product
Technical field
The present invention relates to a kind of method that is used to produce plating moulded product with thin part.More particularly, the present invention relates to a kind of surface and carry out electric plating method, especially a kind of method that is used to produce cellular action button (button) electric or electronic devices and components (as the keyboard top etc. of switch and control Personal Computer), office automation (OA) equipment (as Personal Computer and phone etc.) and signal equipment (as DVD and MD etc.).
Background technology
For example, reducing to exist ever-increasing demand aspect collapsible (flip-shell) cellular thickness.For this cell phone, the action button (button) that connects thereon needs thin as much as possible.
In general, action button is by being easy to molded the forming of galvanized ABS resin (acrylonitrile-butadiene-styrene copolymer).Yet ABS resin is bonded to the poor-performing on the cell phone body.In addition, for the purpose that realizes decorating, action button has a part and is not electroplated.In this case, can except that ABS resin, also use resin to carry out common injection-molded such as PC (polycarbonate) resin.In addition, for the purpose that realizes decorating, wet look (minute surface) and delustering face (coarse a little surface) are set possibly on the plate surface of action button.
Say that traditionally by molded when producing cellular action button, the action button of gained presents unclarity and bright effect.For fear of this situation, after the injection-molded surface of moulded product is electroplated altogether above-mentioned.
In addition, when altogether injection-molded is produced thin moulded product, usually with higher injection speed with resin injection in die cavity.If the injection speed of resin is slower, resin can not enter into die cavity so, and the moulded product that can't obtain approaching.Yet injection speed has caused the problem that coating can come off from the gained moulded product faster.The surface that the reason of this problem is considered to moulded product lacks the ability that coating is fixed thereon, and this depends on resin mobile or directed in molded.
Therefore, come off, proposed after forming metal plating, to form copper coating by electroplating again by electroless plating in order to prevent coating.Traditional copper coating has very strong homogenizing effect, has caused following problems.
In conventional art, even when coarse a little (as the matt finish) that formed action button surperficial, this uneven surface also can be electroplated homogenizing and be produced light, thereby the anchor forfeiture.
Copper is electroplated has the characteristic (level and smooth performance) that can flatten face, therefore, can not reappear condition of surface by the product that is molded into precision die, promptly can't obtain (i) and have minute surface part and the (sandblast (particle finishing) of machining part, hairline finishing etc.) product, the product that for example requires the high precision outward appearance is (as cellular action button, the action button of household electrical appliance etc.) etc., and the product that (ii) requires accurate outward appearance and enhanced contrast gradient, for example precision machined product (as having the product that gets out pattern (sharp-pointed breach), household electrical appliance such as digital video machine etc. on the surface within it of adopting the electroforming mould to be molded into).
Summary of the invention
According to an aspect of the present invention, provide a kind of being used to produce the method for electroplating moulded product, wherein the surface of this moulded product will be electroplated.The method comprising the steps of: (a) form metal plating by electroless plating on the surface of moulded product; (b) on the surface of electroless plating coating, form first nickel coating by electroplating under the following conditions: first nickel plating bath contain 120g/L (grams per liter) to the single nickel salt of 200g/L, 45g/L to 90g/L nickelous chloride and 25g/L to the boric acid of 50g/L, and has a pH value of 3.7 to 4.6, the temperature of plating bath is 46 ℃ to 56 ℃, and cathode current density is 1.0A/dm 2(ampere/square decimeter) is to 3.5A/dm 2(c) on the surface of first nickel coating, form second nickel coating by electroplating under the following conditions: second nickel plating bath contain 200g/L to the single nickel salt of 280g/L, 45g/L to 90g/L nickelous chloride and 25g/L to the boric acid of 50g/L, and has a pH value of 3.7 to 4.6, the temperature of plating bath is 42 ℃ to 56 ℃, and cathode current density is 1.5A/dm 2To 6.0A/dm 2And (d) on the surface of second nickel coating, form the 3rd nickel coating by electroplating under the following conditions: the 3rd nickel plating bath contain 200g/L to the single nickel salt of 280g/L, 45g/L to 90g/L nickelous chloride and 25g/L to the boric acid of 50g/L, and has a pH value of 3.7 to 4.6, the temperature of plating bath is 42 ℃ to 56 ℃, and cathode current density is 1.5A/dm 2To 6.0A/dm 2
According to a further aspect in the invention, provide a kind of method of electroplating moulded product that is used to produce, wherein the surface with the thin part that obtains by injection-molded altogether of this moulded product will be electroplated.The method comprising the steps of: (a) form metal plating by electroless plating on the surface of moulded product; (b) on the surface of electroless plating coating, form first nickel coating by electroplating under the following conditions: first nickel plating bath contain 120g/L to the single nickel salt of 200g/L, 45g/L to 90g/L nickelous chloride and 25g/L to the boric acid of 50g/L, and has a pH value of 3.7 to 4.6, the temperature of plating bath is 46 ℃ to 56 ℃, and cathode current density is 1.0A/dm 2To 3.5A/dm 2(c) on the surface of first nickel coating, form second nickel coating by electroplating under the following conditions: second nickel plating bath contain 200g/L to the single nickel salt of 280g/L, 45g/L to 90g/L nickelous chloride and 25g/L to the boric acid of 50g/L, and has a pH value of 3.7 to 4.6, the temperature of plating bath is 42 ℃ to 56 ℃, and cathode current density is 1.5A/dm 2To 6.0A/dm 2And (d) on the surface of second nickel coating, form the 3rd nickel coating by electroplating under the following conditions: contain in the 3rd nickel plating bath 200g/L to the single nickel salt of 280g/L, 45g/L to 90g/L nickelous chloride and 25g/L to the boric acid of 50g/L, and has a pH value of 3.7 to 4.6, the temperature of plating bath is 42 ℃ to 56 ℃, and cathode current density is 1.5A/dm 2To 6.0A/dm 2
In one embodiment of the invention, in second nickel-plating liquid, also added the acetylene alcohol derivative of 0.4% to 1.2% weight.
In one embodiment of the invention, in the 3rd nickel-plating liquid, also added the butyne diol derivatives of 0.4% to 1.6% weight.
In one embodiment of the invention, this product is sent to the step that forms the 3rd nickel coating from the step that forms second nickel coating when electric current therefrom flows through.
In one embodiment of the invention, on the surface of moulded product, be provided with wet look and uneven surface.
According to a further aspect in the invention, provide a kind of plating moulded product that obtains by aforesaid method.
In one embodiment of the invention, this moulded product is the action button that is used for cell phone.
Function of the present invention will be described herein-after.
A feature of nickel plated film is that nickel is along the shape deposition (adaptability) of below.Therefore, can reproduce the condition of surface of the moulded product that is molded into by precision die.Electroplate (trigger nickel and electroplate (strike nickelplating)) by the non-light nickel that after electroless nickel plating, approaches, just can prevent from that the electroless nickel plating film from punishing at the power supply position to separate.
In addition, when being provided with double-deck bright nickel layer (half bright layer and bright layer), by with specific technology electric current being flow through when second nickel-plating liquid is sent to the 3rd nickel-plating liquid product, just can prevent half bright layer and bright layer come off each other (adhesivity deficiency) from product.
When product when second nickel-plating liquid under having different bath compositions and being in different plating conditions is sent to the 3rd nickel-plating liquid, be exposed in the air as fruit product, the nickel film is will be in air oxidized and form oxide film so.For this reason, the nickel film that forms by electroplating in the 3rd nickel-plating liquid just comes off probably.According to the present invention, product when being sent to the 3rd nickel-plating liquid, second nickel-plating liquid is made electric current flow through from the utensil that is used for clamping and transmission product.Like this, just can prevent from the surface of second nickel layer, to form oxide film, and prevent that the 3rd nickel layer from coming off.
Afterwards, be plated in by electricity consumption and form chromium layer or chromium alloy layer on the surface of the 3rd nickel layer, just metal plating can be sticked on the underlying surface securely, even therefore for having thin moulded product partly, this metal plating also can be resisted and come off.In addition, when the surperficial enterprising electroplating of the moulded product that is provided with wet look and matte surface thereon, reproducibility is gratifying.
Measure the easiness of removing the coating on the moulded product under the following conditions.
Quadrature cementation test: take advantage of 1 millimeter intersection to cut out the zone for 1 millimeter.
Thermal shock test: repeat the circulation of 85 ℃, 1 hour and-35 ℃, 1 hour.Coating need still remain intact after 6 or more a plurality of circulation.Traditional coating is just destroyed after 3 circulations.
Therefore, here the invention of Jie Shaoing can provide such advantage, a kind of method of electroplating moulded product that is used to produce promptly is provided, it can provide can resist the coating that comes off and can reproduce unglazed underlying surface, even concerning also being like this by the molded moulded product with thin part that obtains of high speed injection.
With reference to accompanying drawing and after reading and having understood following detailed introduction, those skilled in the art can know these and other advantage of the present invention.
Description of drawings z
Fig. 1 is the sectional view that has shown the representativeness plating moulded product that obtains by the method according to this invention.
Embodiment
To introduce the present invention with reference to the accompanying drawings and by illustrated examples hereinafter.
As shown in Figure 1, thin moulded product 4 according to the present invention comprises by being total to the thin part 3 that injection-molded is produced.In addition, Bao moulded product 4 comprises second moulded product 2 on first moulded product 1 that is formed by ABS resin and the inboard that is overmolded to first moulded product 1 by common injection-molded.Second moulded product 2 can be formed by transparent resin such as PC.
This have thin part 3 (cast gate) by the molded dish type product 4 that obtains of high speed injection, and its thickness is generally 0.35 millimeter or littler, is preferably 0.15 to 0.30 millimeter.In order to provide shape the moulded product more complicated and exquisiter than conventional molded components, this product is by injection molding process is molded altogether, and die cavity and core reverse in this method.Owing to be provided with thin part, so injection speed faster than routine.Fast injection is molded to mean that being oriented in of butadiene molecule produced variation in the ABS resin.In other words, for spherical basically, and its shape becomes ellipse to butadiene molecule when speed surpasses certain value under conventional injection speed, so the coating that obtains by conventional art is easy to split away off from the surface of moulded product.
By following step the moulded product with thin part that obtains is like this electroplated, so that at the surperficial enterprising electroplating of moulded product.
(a) after cleaning this moulded product, on the surface of moulded product, do not form metal plating by there being electric formula nickel plating (electroless plating).
Electroless plating is carried out in the following manner:
Corrosion step: moulded product is immersed in is in containing in the chromic anhydride and the vitriolic aqueous solution under the preset temperature, clean afterwards, the surface of moulded product is roughened.
Catalyzer (activator) step: moulded product is immersed in contains in Palladous chloride, tin protochloride and the aqueous solution of hydrochloric acid, clean afterwards, palladium just is adsorbed on the surface of moulded product like this.
The accelerator step: moulded product is immersed in the aqueous hydrochloric acid, cleans afterwards, the tin that therefore in the catalyzer step, adsorbs with palladium by dissolve with hydrochloric acid solution with separate.In this case, palladium is stayed on the ABS resin of common injection-molded product, palladium removal from PC etc. simultaneously.In order to realize this purpose, make the coating bath main body produce bubble under given conditions, thereby prevent at enterprising electroplatings such as PC.
Do not have electric formula nickel plating or do not have electric formula copper facing (electroless plating): moulded product is immersed in the mixture of nickel or copper, formalin, Rochelle salt, sodium hydroxide, sodium hypophosphite, ammonia, water etc., clean afterwards, so nickel or copper just are deposited on the palladium because of the reduction reaction of formalin and sodium hypophosphite.
(b) then, in the following manner at the enterprising electroplating of electroless plating coating.
In the present invention, the plating step of nickel comprises: (1) sulfuric acid activation step, and (2) water-washing step, (3) recycling step, (4) trigger the plating step of nickel, the plating step of (5) semi-bright nickel, and the plating step of (6) bright nickel.
Should be noted in the discussion above that at bright nickel plating step (6) afterwards, carry out the secondary water washing step, carry out the chromium plating step afterwards.
The purpose of each step is as described below.
(1) sulfuric acid activation step: the oxide film of product surface of having removed the covering that generated in pre-treatment step (electroless plating nickel plating), acid activation electroless plating nickel plating surface is to promote the deposition of nickel in the electroplating process of nickel.
(2) water-washing step: flush away increases so that prevent the pH value that triggers nickel because of the adherent aqueous sulfuric acid of sulfuric acid activation step.
(3) recycling step: product is placed sky coating bath for some time, so that water for cleaning flows down from product.
(4) plating step of triggering nickel: before half light/bright nickel is electroplated, on the electroless nickel plating film, form no bright nickel film (thickness is preferably about 1 micron to about 2 microns).
The reason of this step is: the deposition that (i) needs to promote the semi-bright nickel in the subsequent step; And (ii) when when applying big electric current (4 to 6 volts) and come that the electroless nickel plating film directly carried out the plating of semi-bright nickel, the electroless nickel plating film can dissolve, and electrically contacts like this and built on the sand; Therefore need trigger the plating of nickel.
(5) plating step of semi-bright nickel: the nickel film (thickness is preferably about 3 microns to about 7 microns) that forms half light (low-light level) with higher covering power.
The reason of this step is the deposition that need promote bright nickel in subsequent step, so that can easily obtain the effect of light.
(6) plating step of bright nickel: form light (high brightness) nickel (thickness is preferably about 3 microns to about 7 microns) with brightness effect.
The reason of this step is to need to reproduce the brightness effect that can satisfy user's demand.
Therefore, in the present invention, form three layers or more coating by the nickel plating step.Because the plating of nickel has extraordinary adaptability, thus the carrying out of moulded product a part of original surface of sandblast (particle finishing, hairline finishing, butler finish, engraving finishing) in statu quo form the protuberance and the projection of sandblast pattern (particle finishing, hairline finishing, butler finish, engraving finishing).And flat (glossy surface) has and resulting the same brightness effect traditionally.
Afterwards, on the surface of nickel coating, form chromium layer or chromium alloy layer by electroplating.
To introduce the plating condition in each step below.
(1) the plating condition in the plating step (forming the step of first nickel layer) of triggering nickel:
The concentration of single nickel salt be 120g/L to 200g/L, be preferably 150g/L to 190g/L.If the concentration of single nickel salt is lower than 120g/L, the covering power of plated film descends so.If the concentration of single nickel salt is higher than 200g/L, plated film can become coarse so.
The concentration of nickelous chloride be 45g/L to 90g/L, be preferably 50g/L to 80g/L.If the concentration of nickelous chloride is lower than 45g/L, the covering power of plated film descends so.If the concentration of nickelous chloride is higher than 90g/L, plated film can become more crisp so.
The concentration of boric acid be 25g/L to 50g/L, be preferably 35g/L to 45g/L.If the concentration of boric acid is lower than 25g/L, the pH value will increase so.If the concentration of boric acid is higher than 50g/L, plated film can become coarse so.
The pH value of nickel plating bath is 3.7 to 4.6, is preferably 3.8 to 4.3.If the pH value of plating bath is lower than 3.7, the covering power of plated film can variation so.If the pH value of plating bath is higher than 4.6, may produce concave point (vestige of the hydrogen that electrolytic reaction produced) so.
The temperature of plating bath is 46 ℃ to 56 ℃, is preferably 48 ℃ to 56 ℃.If the temperature of plating bath is lower than 46 ℃, the covering power of plated film can variation so.If the temperature of plating bath is higher than 56 ℃, in folding corner region, can produce a lot of burnt deposits (abnormal deposition) defective so.
Cathode current density is 1.0A/dm 2To 3.5A/dm 2, be preferably 2A/dm 2To 3A/dm 2If cathode current density is lower than 1.0A/dm 2, the covering power of plated film can descend so.If cathode current density is higher than 3.5A/dm 2, in folding corner region, can produce a lot of burnt deposits (abnormal deposition) defective so.
(2) the plating condition in the plating step of semi-bright nickel (forming the step of second nickel layer):
The concentration of single nickel salt be 200g/L to 280g/L, be preferably 220g/L to 260g/L.If the concentration of single nickel salt is in outside this scope, will produce and form the above-mentioned steps similar problem of first nickel layer.
The concentration of nickelous chloride be 45g/L to 90g/L, be preferably 50g/L to 70g/L.If the concentration of nickelous chloride is in outside this scope, will produce and form the above-mentioned steps similar problem of first nickel layer.
The concentration of boric acid be 25g/L to 50g/L, be preferably 35g/L to 45g/L.If the concentration of boric acid is in outside this scope, will produce and form the above-mentioned steps similar problem of first nickel layer.
The pH value of nickel plating bath is 3.7 to 4.6, is preferably 3.8 to 4.3.If this pH value is in outside this scope, will produce and form the above-mentioned steps similar problem of first nickel layer.
The temperature of plating bath is 42 ℃ to 56 ℃, is preferably 44 ℃ to 53 ℃.If the temperature of plating bath is in outside this scope, will produce and form the above-mentioned steps similar problem of first nickel layer.
Cathode current density is 1.5A/dm 2To 6.0A/dm 2, be preferably 3.5A/dm 2To 5.5A/dm 2If cathode current density is in outside this scope, will produce and form the above-mentioned steps similar problem of first nickel layer.
Be preferably in interpolation 0.4% to 1.2% weight in second nickel-plating liquid, be preferably the acetylene alcohol derivative of 0.6% to 1.0% weight as additive.If it is lower that the amount of additive, produces the effect and the brightness of uniform galvanic deposit ability so less than 0.4% weight.If the amount of additive is greater than 1.2% weight, brightness plated film too high and gained becomes fragile so.The example of acetylene alcohol derivative comprises non-homogenizing nickel plating brightener.
(3) the plating condition in the plating step of bright nickel (forming the step of the 3rd nickel layer):
The concentration of single nickel salt be 200g/L to 280g/L, be preferably 220g/L to 260g/L.If the concentration of single nickel salt is in outside this scope, will produce and form the above-mentioned steps similar problem of first nickel layer.
The concentration of nickelous chloride be 45g/L to 90g/L, be preferably 50g/L to 70g/L.If the concentration of nickelous chloride is in outside this scope, will produce and form the above-mentioned steps similar problem of first nickel layer.
The concentration of boric acid be 25g/L to 50g/L, be preferably 35g/L to 45g/L.If the concentration of boric acid is in outside this scope, will produce and form the above-mentioned steps similar problem of first nickel layer.
The pH value of nickel plating bath is 3.7 to 4.6, is preferably 3.8 to 4.3.If this pH value is in outside this scope, will produce and form the above-mentioned steps similar problem of first nickel layer.
The temperature of plating bath is 42 ℃ to 56 ℃, is preferably 44 ℃ to 53 ℃.If the temperature of plating bath is in outside this scope, will produce and form the above-mentioned steps similar problem of first nickel layer.
Cathode current density is 1.5A/dm 2To 6.0A/dm 2, be preferably 3.5A/dm 2To 5.5A/dm 2If cathode current density is in outside this scope, will produce and form the above-mentioned steps similar problem of first nickel layer.
Be preferably in interpolation 0.4% to 1.6% weight in the 3rd nickel-plating liquid, be preferably the butyne diol derivatives of 0.6% to 1.1% weight as additive.If it is lower that the amount of additive, produces the effect of uniform galvanic deposit ability, reduction internal stress and raising corrosion resistance nature so less than 0.4% weight.If it is too high that the amount of additive, then can produce brightness greater than 1.6% weight, and because of remaining additive meeting generation defective (for example burnt deposit, spot etc.) in subsequent step.The example of butyne diol derivatives comprises bright nickel coating brightening agent etc.
According to first invention, even can resist the coating that comes off for having moulded product, also can accessing by the molded thin part that obtains of high speed injection.In addition, even when when forming coating on the surface of handling through particle finishing, hairline finishing, butler finish or engraving finishing, coating also can reproduce the surface of handling through particle finishing, hairline finishing, butler finish or engraving finishing.
Traditional copper is electroplated has very strong leveling effect, thereby has following problems.Even small roughness is provided from the teeth outwards, when for example particle finishing, hairline finishing, butler finish or engraving finishing, this roughness also can be electroplated leveling and too high brightness is provided, and therefore can't reproduce the effect of handling through particle finishing, hairline finishing, butler finish or engraving finishing.Therefore, the feature of electroforming die cavity is destroyed.
On the contrary, the present invention carries out under specific plating condition, make metal plating can stick to securely on the underlying surface and can resist to come off, and also be like this even have when approaching part at moulded product.In addition, this plating can be reproduced the glossy surface of moulded product and the surface of handling through particle finishing, hairline finishing, butler finish or engraving finishing.
In addition, compare with having the underlie product of copper coating of tradition, the product that obtains according to the present invention does not have the peculiar defective of copper coating (for example ununiformity adheres to foreign matter (projection)).In the present invention, nickel deposition (nickel deposition is on nickel) rather than be deposited on the another kind of metal on metalloid.Therefore, consistency and adhesivity between the layer all are gratifying, thereby can cancel special neutralizationization and cleaning step between the plating step of the plating step of copper and nickel.According to these advantages, to compare with having the product that is positioned at the copper coating on the underlying surface, the output with product of required quality has on average improved 20%, can improve 30% or more in some cases.
Under the prerequisite that does not depart from the scope of the present invention with spirit, those skilled in the art can know and easily the present invention be carried out various other modifications.Therefore, the specification sheets that the scope of claims is not limited to here to be proposed on the contrary, should be understood claim in a broad sense.

Claims (8)

1. one kind is used to produce the method for electroplating moulded product, and the surface of wherein said moulded product will be electroplated, and described method comprises step:
(a) on the surface of described moulded product, form metal plating by electroless plating;
(b) on the surface of described electroless plating coating, form first nickel coating by electroplating under the following conditions: first nickel plating bath contain 120g/L to the single nickel salt of 200g/L, 45g/L to 90g/L nickelous chloride and 25g/L to the boric acid of 50g/L, and has a pH value of 3.7 to 4.6, the temperature of described plating bath is 46 ℃ to 56 ℃, and cathode current density is 1.0A/dm 2To 3.5A/dm 2
(c) on the surface of described first nickel coating, form second nickel coating by electroplating under the following conditions: second nickel plating bath contain 200g/L to the single nickel salt of 280g/L, 45g/L to 90g/L nickelous chloride and 25g/L to the boric acid of 50g/L, and has a pH value of 3.7 to 4.6, the temperature of described plating bath is 42 ℃ to 56 ℃, and cathode current density is 1.5A/dm 2To 6.0A/dm 2With
(d) on the surface of described second nickel coating, form the 3rd nickel coating by electroplating under the following conditions: the 3rd nickel plating bath contain 200g/L to the single nickel salt of 280g/L, 45g/L to 90g/L nickelous chloride and 25g/L to the boric acid of 50g/L, and has a pH value of 3.7 to 4.6, the temperature of described plating bath is 42 ℃ to 56 ℃, and cathode current density is 1.5A/dm 2To 6.0A/dm 2
2. one kind is used to produce the method for electroplating moulded product, and the surface with the thin part that obtains by injection-molded altogether of wherein said moulded product will be electroplated, and described method comprises step:
(a) on the surface of described moulded product, form metal plating by electroless plating;
(b) on the surface of described electroless plating coating, form first nickel coating by electroplating under the following conditions: first nickel plating bath contain 120g/L to the single nickel salt of 200g/L, 45g/L to 90g/L nickelous chloride and 25g/L to the boric acid of 50g/L, and has a pH value of 3.7 to 4.6, the temperature of described plating bath is 46 ℃ to 56 ℃, and cathode current density is 1.0A/dm 2To 3.5A/dm 2
(c) on the surface of described first nickel coating, form second nickel coating by electroplating under the following conditions: second nickel plating bath contain 200g/L to the single nickel salt of 280g/L, 45g/L to 90g/L nickelous chloride and 25g/L to the boric acid of 50g/L, and has a pH value of 3.7 to 4.6, the temperature of described plating bath is 42 ℃ to 56 ℃, and cathode current density is that 1.5A/dm2 is to 6.0A/dm2; With
(d) on the surface of described second nickel coating, form the 3rd nickel coating by electroplating under the following conditions: the 3rd nickel plating bath contain 200g/L to the single nickel salt of 280g/L, 45g/L to 90g/L nickelous chloride and 25g/L to the boric acid of 50g/L, and has a pH value of 3.7 to 4.6, the temperature of described plating bath is 42 ℃ to 56 ℃, and cathode current density is 1.5A/dm 2To 6.0A/dm 2
3. method according to claim 1 and 2 is characterized in that, described second nickel-plating liquid also is added with the acetylene alcohol derivative of 0.4% to 1.2% weight.
4. according to each described method in the claim 1 to 3, it is characterized in that described the 3rd nickel-plating liquid also is added with the butyne diol derivatives of 0.4% to 1.6% weight.
5. according to each described method in the claim 1 to 4, it is characterized in that described product is sent to the step of described formation the 3rd nickel coating from the step of described formation second nickel coating when electric current therefrom flows through.
6. according to each described method in the claim 1 to 5, it is characterized in that, on the surface of described moulded product, be provided with wet look and uneven surface.
7. plating moulded product by obtaining according to each described method in the claim 1 to 6.
8. plating moulded product according to claim 7 is characterized in that, described moulded product is the action button that is used for cell phone.
CNB2004100082949A 2003-02-26 2004-02-26 Method for producing molded goods plating Expired - Fee Related CN1297693C (en)

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CN102719868A (en) * 2012-07-20 2012-10-10 滨中元川金属制品（昆山）有限公司 Nickel plating process of stainless steel fastener
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JP4896703B2 (en) * 2006-12-26 2012-03-14 東海ゴム工業株式会社 Nickel electroplating film and its manufacturing method
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CN102330133A (en) * 2011-07-27 2012-01-25 太仓市金鹿电镀有限公司 Technology for evenly and continuously plating nickel
CN102719868A (en) * 2012-07-20 2012-10-10 滨中元川金属制品（昆山）有限公司 Nickel plating process of stainless steel fastener
CN102719868B (en) * 2012-07-20 2015-07-29 滨中元川金属制品（昆山）有限公司 A kind of nickel plating technology of stainless steel support
CN106130218A (en) * 2016-07-05 2016-11-16 扬州市新港电机有限公司 The automobile-used flux switch permanent magnet motor of integrated electric
CN106130218B (en) * 2016-07-05 2018-03-30 扬州市新港电机有限公司 A kind of electric car flux switch permanent magnet motor

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JP2004256876A (en) 2004-09-16
TW200500505A (en) 2005-01-01

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