CN101396890A - Plastics products and preparation method thereof - Google Patents
Plastics products and preparation method thereof Download PDFInfo
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- CN101396890A CN101396890A CNA2007101517922A CN200710151792A CN101396890A CN 101396890 A CN101396890 A CN 101396890A CN A2007101517922 A CNA2007101517922 A CN A2007101517922A CN 200710151792 A CN200710151792 A CN 200710151792A CN 101396890 A CN101396890 A CN 101396890A
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Abstract
The invention relates to a plastic product, comprising plastic substrate. The plastic product is characterized in that the product also comprises a copper coating, a nickel coating, a chrome coating and a ceramic coating from the surface of the plastic substrate to the outside in sequence; the ceramic coating is one or more layer of titanium nitride, titanium carbide and titanium carbonitride. The plastic product made by the invention has excellent wearing resistance, the film formed on the surface of the plastic product has excellent adhesiveness, and the plastic product that is obtained finally also has ceramic texture and good handfeel.
Description
Technical field
The present invention relates to a kind of plasthetics and preparation method thereof.
Background technology
At present, the raw material of preparation plasthetics generally includes thermoplastic and thermosetting plastics, and described thermoplastic for example can be one or more in acrylonitrile-butadiene-styrene (ABS) (ABS), polypropylene (PP), nylon (PA), polytetrafluoroethylene (PTFE), polyformaldehyde (POM), polyethylene (PE), polyvinyl chloride (PVC), polystyrene (PST), polysulfones (PSF), polyphenylene oxide (PPO), PET (PET), Merlon (PC) and the polymethyl methacrylate (PMMA); Described thermosetting plastics for example can be phenoplasts and/or epoxy plastics.In addition, described plastic rubber substrate can also comprise that routine is used for the performance of the various additives of plastic rubber substrate with the raising plastic rubber substrate, for example can add the intensity that glass fibre improves plastic rubber substrate.
The plasthetics of being made by plastic material has advantages such as molding cycle is short, production efficiency is high, in light weight, therefore is subjected to extensive use.But the feel of common plasthetics is general, and brightness is lower, easily wearing and tearing of surface in use, and the texture that does not possess present people and pursued, surcharge is not high.Therefore, the common use more carried out suitable surface-treated plasthetics.
Surface-treated research about plasthetics is less.In the existing method, disclosed the surface property that the method that plastic rubber substrate is carried out surperficial coating composition is improved plasthetics.But the coating adhesion that this method exists coating to form is low, comes off easily, wears no resistance, and shortcoming such as can't use for a long time, and the method for this coating composition, and corresponding different plastic rubber substrate need use different coating, otherwise adhesive force may be poorer.
CN 1459380A also discloses a kind of elder generation's printing back electric plating method that carries out on the plastic cement surface in addition, it is characterized in that this method may further comprise the steps: plastic rubber substrate is carried out pre-treatment, print then, carry out electroplating processes again.
But no matter the plasthetics that obtains through above-mentioned processing is at surface abrasion resistance, still all is still waiting to improve further on aesthetic property and feel.
Summary of the invention
The objective of the invention is that plastic rubber substrate surface feel is poor, brightness is low, the shortcoming of easy wearing and tearing, and plasthetics of a kind of good hand touch, brightness height and high abrasion resistance and preparation method thereof is provided in order to overcome in the prior art.
Usually, the method that forms ceramic layer by physical vaporous deposition is widely used in the metallic article field of surface treatment, and this method can be improved the performance on metallic article surface.But because the goods different in kind, this method is not suitable for using on plastic rubber substrate.And the present inventor is by research, realized at plastic rubber substrate surface plating ceramic layer, thereby made full use of the good surface property of ceramic layer, improved the performance of plastic rubber substrate, and expanded the range of application of carrying out surface ceramic deposition by physical vaporous deposition.
The invention provides a kind of plasthetics, these goods comprise plastic rubber substrate, wherein, these goods outwards also comprise copper layer, nickel dam, chromium layer and ceramic layer successively from the plastic rubber substrate surface, and one deck in titanium nitride layer, titanium carbide layer and the titanium carbonitride layer or which floor described ceramic layer be.
The present invention also provides a kind of preparation method of plasthetics, wherein, this method is included in the plastic rubber substrate surface and forms copper layer, nickel dam and chromium layer successively, forms ceramic layer then on the chromium layer, and one deck in titanium nitride layer, titanium carbide layer and the titanium carbonitride layer or which floor described ceramic layer be.
The high abrasion resistance of the plasthetics that the present invention makes, and the rete that the plastic cement surface forms has good adhesive force.For example, the rete of plasthetics of the present invention does not see behind 350 circles that in RCA paper tape wearability test base material is exposed, carries out the adhesive force test result by hundred lattice cuttves in addition and is 0 grade.And the plasthetics that the present invention finally obtains has the texture of pottery, good hand touch.
The specific embodiment
Goods provided by the invention comprise plastic rubber substrate, and wherein, these goods outwards also comprise copper layer, nickel dam, chromium layer and ceramic layer successively from the plastic rubber substrate surface, and one deck in titanium nitride layer, titanium carbide layer and the titanium carbonitride layer or which floor described ceramic layer be.
The thickness of described copper layer can be the 5-15 micron, is preferably the 6-10 micron; The thickness of described nickel dam can be the 5-30 micron, is preferably the 10-20 micron; The thickness of described chromium layer can be the 5-30 micron, is preferably the 10-20 micron.The thickness of described ceramic layer is the 0.1-2 micron, is preferably the 0.2-1 micron.
Under the situation more than described ceramic layer has two-layer in titanium nitride layer, titanium carbide layer and the titanium carbonitride layer, as long as the thickness sum of each layer is in the thickness range of described ceramic layer, the thickness of each layer can be any thickness.
Described plastic rubber substrate can be the plastic rubber substrate that the various plastic materials by routine form, and described plastic material all can be commercially available.In order to improve the adhesive force of copper layer on plastic rubber substrate, under the preferable case, described plastic rubber substrate is for electroplating the level plastic rubber substrate.Described plating level plastic rubber substrate is conventionally known to one of skill in the art, is meant by electroplating the plastic rubber substrate that the level plastic material forms.Described plating level plastic material comprises to be electroplated the grade thermoplastic plastics or electroplates the level thermosetting plastics.Described plating grade thermoplastic plastics comprise electroplates level acrylonitrile-butadiene-styrene (ABS), electroplate grade polypropylene (PP), electroplate level nylon (PA), electroplate the level polytetrafluoroethylene (PTFE), electroplate level polyformaldehyde (POM), electroplate level polyethylene (PE), electroplate grade PVC (PVC), electroplate polystyrene (PST), electroplate level polysulfones (PSF), electroplate grade polycarbonate (PC), electroplate level polyphenylether (PPO), in plating level PET (PET) and the plating grade polymethylmethacrylacontinuous (PMMA) one or more; Described plating level thermosetting plastics comprises to be electroplated the level phenoplasts and/or electroplates the level epoxy plastics.Described plating grade thermoplastic plastics or a plating level thermosetting plastics all can be commercially available.In addition, described plastic rubber substrate can also comprise that routine is used for the performance of the various additives of plastic rubber substrate with the raising plastic rubber substrate, for example can add the intensity that glass fibre improves plastic rubber substrate.
The preparation method of plasthetics of the present invention is included in the plastic rubber substrate surface and forms copper layer, nickel dam and chromium layer successively, forms ceramic layer then on the chromium layer, and one deck in titanium nitride layer, titanium carbide layer and the titanium carbonitride layer or which floor described ceramic layer be.
Described copper layer, nickel dam and chromium layer can form by conventional the whole bag of tricks, for example can form by the method for physical vapour deposition (PVD), also can form by electric plating method.
Consider that from the angle of the tack of coating and plastic rubber substrate the present invention preferably forms described copper layer, nickel dam and chromium layer by electric plating method.The condition of described plating is as long as the thickness of the feasible copper layer that forms is the 5-15 micron, the thickness of nickel dam is the 5-30 micron, the thickness of chromium layer gets final product for the 5-30 micron, the thickness of the feasible copper layer that forms of the condition of preferred described plating is the 6-10 micron, the thickness of nickel dam is the 10-20 micron, and the thickness of chromium layer is the 10-20 micron.
The method that described plating forms the copper layer is conventionally known to one of skill in the art.This method comprises that the plastic rubber substrate with conduction is a negative electrode, is anode with copper or insoluble conductor, electroplates in electroplate liquid, and described electroplate liquid is an acid copper plating solution, and the temperature of described plating is 5-40 ℃, and current density is 0.5-8A/dm
2, the time of plating is 10-30 minute.Wherein, the plastic rubber substrate of described conduction is the plastic rubber substrate through surface catalysis.The method of described surface catalysis is conventionally known to one of skill in the art.For example, described plastic rubber substrate can be flooded 4-10 minute in catalytic liquid under 30-40 ℃.Described catalytic liquid is the catalyst (the CRP CATALYST K that the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces) that contains 25-40mL/L, the palladium ion of 170-270mg/L, the additive (the CRP CATALYST additive that the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces) of 20-100mL/L and the 35 volume % aqueous solution of hydrochloric acid of 200-300mL/L.In addition, described insoluble conductor for example can be stainless steel or graphite.
Described acid copper plating solution is the aqueous solution of the COPPER A (production of the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou) of the COPPER MU (the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces) of chlorion, 3-7mL/L of sulfuric acid, the 50-100mg/L of the copper sulphate that contains 180-200g/L, 30-70g/L and 0.3-0.7mL/L.
Under the preferable case, before carrying out above-mentioned surface catalysis, earlier described plastic rubber substrate is carried out degreasing, surperficial adjustment, alligatoring, neutralization and preimpregnation successively.
Described degreasing is to clean the plasthetics surface with degreasing fluid, to remove the dirts such as oil stain on the plasthetics, the kind of described degreasing fluid and consumption are conventionally known to one of skill in the art, the CRP CLEANER that for example can use the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou to produce, the described oil temperature of removing can be 40-80 ℃, and the time of oil removing was generally 3-15 minute.
Described surface adjustment is that described plastic rubber substrate is adjusted dipping 1-5 branch in the liquid on 40-60 ℃ surface, and it is the aqueous solution that contains the sulfuric acid of 20-40ml/L, the surfactant of 3-20ml/L (the CRP UNIPLA that the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces) that liquid is adjusted on described surface.
Described alligatoring is that described plastic rubber substrate is flooded the 5-10 branch in 65-70 ℃ coarsening solution, and described coarsening solution is sulfuric acid, 0.4-1.4 milliliter/the rise aqueous solution of the trivalent chromic ion of additive (the CRP alligatoring additive that the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces), 5-30g/L of the chromic anhydride that contains 380-420g/L, 380-450g/L.
Described neutralization is to flood in 20-30 ℃ neutralizer 30-90 second through the plastic rubber substrate after the alligatoring, described neutralizer is the aqueous solution of the CRP NEUTRALIZER 300 that contains 10-30mL/L (the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces), and the pH value of described neutralizer is 10-12.
Described preimpregnation is to flood 10-60 second in 15-30 ℃ presoak through the plastic rubber substrate after the neutralisation treatment, and described presoak is the 35 volume % aqueous solution of hydrochloric acid that contain 150-250mL/L.
Described activation is that the plasthetics through preimpregnation was flooded 5-10 minute in 10-30 ℃ activating solution, and described activating solution is the aqueous solution, contains the PdCl of 0.5-1.0g/L
2, 30-40mL/L 35 volume %HCl.
The method that described plating forms nickel dam comprises, is negative electrode with the plastic rubber substrate that is formed with the copper layer, is anode with nickel or insoluble conductor, electroplates in electroplate liquid, and described electroplate liquid is a nickel plating bath, and the temperature of described plating is 30-55 ℃, and current density is 2-10A/dm
2, the time of plating is 5-15 minute.Described insoluble conductor for example can be stainless steel or graphite.Described nickel plating bath is the nickelous sulfate that contains 250-320g/L, the nickel chloride of 50-60g/L, the boric acid of 40-50g/L, the aqueous solution of 0.1-1.0mL/L additive (the ACNA HSB that the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces), and the pH value of described nickel plating bath is 3.8-4.4.
Under the preferable case, after carrying out above-mentioned electronickelling, described plastic rubber substrate is carried out the nickel envelope handle.The method that described nickel envelope is handled comprises: being negative electrode with the plastic rubber substrate, is anode with nickel or insoluble conductor, electroplates in electroplate liquid, and described electroplate liquid is the nickel sealing liquid, and the temperature of described plating is 40-60 ℃, and current density is 0.5-2.5A/dm
2, the time of plating is 0.5-2.5 minute.Described insoluble conductor for example can be stainless steel or graphite.Described nickel envelope plating bath is the aqueous solution of additive (the SMPC SERIES that the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces) of nickel envelope powder, the 0.1-2.0mL/L of boric acid, the 15-20g/L of nickel chloride, the 40-48g/L of the nickelous sulfate that contains 200-250g/L, 50-90g/L, and the pH value of described nickel sealing liquid is 3.9-4.4.Described nickel envelope powder can be commercially available.
The method that described plating forms the chromium layer comprises, is negative electrode with the plastic rubber substrate that is formed with copper layer and nickel dam, is anode with chromium or insoluble conductor, in electroplate liquid, electroplate, described electroplate liquid is the chromium plating bath, and the temperature of described plating is 40-60 ℃, and current density is 20-35A/dm
2, the time of plating is 5-15 minute.Described insoluble conductor for example can be stainless steel or graphite.Described chromium plating bath is the aqueous solution of the trivalent chromic ion of sulfuric acid, the 3-6g/L of the chromic anhydride that contains 230-270g/L, 2.2-2.9g/L, the fog inhibitor of 0.03-0.05mL/L (auspicious phase fine chemistry Engineering Co., Ltd produce RM-118 X).
In addition, between each step, preferably described plastic rubber substrate is washed, the temperature of described washing is 5-25 ℃, and the time of washing is 0.5-2 minute.
This plastic rubber substrate is being washed dryly then after forming the chromium layer on the plastic rubber substrate, described drying can natural air drying, also can 40-80 ℃ dry 10-20 minute down.
Described ceramic layer forms by physical vaporous deposition, and described physical vaporous deposition for example can be vacuum evaporation coating method, vacuum sputtering plating method or vacuum ion plating method.The concrete operations of said method and condition have been conventionally known to one of skill in the art.
The method that the present invention forms described ceramic layer is preferably vacuum sputtering plating method, described vacuum sputtering plating method is included under the condition of vacuum sputtering plating, with inert gas as working gas, with nitrogen and/or acetylene as reacting gas, make titanium as target become titanium nitride and/or titanium carbide with nitrogen and/or acetylene reaction and be deposited on the chromium layer of plastic rubber substrate and form ceramic layer, described inert gas is a zero group gas, is preferably argon gas.The condition of described vacuum sputtering plating makes the thickness of described ceramic layer get final product for the 0.1-2 micron, and it is the 0.2-1 micron that the condition of preferred described vacuum sputtering plating makes the thickness of described ceramic layer.
Described vacuum sputtering plating can be implemented by the vacuum sputtering coating machine.Described vacuum sputtering coating machine can be commercially available.Different vacuum sputtering coating machines reaches identical ceramic layer thickness corresponding condition and has difference.But in order to reach the coating of thickness of the present invention, generally speaking, can carry out vacuum sputtering plating according to following condition: it is 1 * 10 that the plastic rubber substrate that will be formed with the chromium layer places vacuum
-2-8 * 10
-2In the vacuum chamber of handkerchief, carry out radio frequency with oxygen and clean, the power of described radio frequency is 600-900 watt, and the time of described cleaning is 1-6 minute; Then 2 * 10
-3-5 * 10
-3Under the vacuum of handkerchief, feed the inert gas as working gas, feed nitrogen and/or acetylene as reacting gas simultaneously, wherein, the consumption of described inert gas and reactant gas is conventionally known to one of skill in the art.This inert gas is ionized the back and under electric field action the titanium as target is carried out vacuum sputtering, the titanium of described vacuum sputtering and reacting gas reaction generation titanium nitride, titanium carbide or titanium carbonitride, and deposit on the described plastic rubber substrate and form ceramic layer.The power of described vacuum sputtering is 8.5-9.5 kilowatt, and the distance of described target and plastic rubber substrate is 5-10 centimetre, and the time of vacuum sputtering is 4-10 minute.In addition, need to prove that above-mentioned vacuum sputtering can carry out repeatedly, thus can form have titanium nitride layer, the two-layer above ceramic layer in titanium carbide layer and the titanium carbonitride layer, as long as with the THICKNESS CONTROL of described ceramic layer at the 0.1-2 micron.
In addition, the kind of described plastic rubber substrate is narrated in the above, repeats no more herein.Described plastic rubber substrate can form by conventional method.The method of described injection mo(u)lding is conventionally known to one of skill in the art.For example can form by the injection moulding machine injection moulding.Described injection moulding machine can be commercially available.
In addition, plasthetics of the present invention can adopt different plastic materials to make as required, and can make different shape by the method for routine, for example can make electronic product casing, ornament, plastic packing box, electric equipment products shells etc. such as mobile phone.
Below by embodiment the present invention is illustrated in greater detail.
Embodiment 1
Present embodiment illustrates plasthetics of the present invention and preparation method thereof.
To electroplate level acrylonitrile-butadiene-styrene and Merlon complex plastic material (the C1200HF-GY7B080U LEXAN of GE) as raw material (weight ratio of acrylonitrile-butadiene-styrene (ABS) and Merlon is about 7: 3), carry out injection mo(u)lding with injection moulding machine, obtain plastic rubber substrate.
This plastic rubber substrate is handled according to following operation successively:
Degreasing → washing → surface adjustment → washing → alligatoring → washing → neutralization → washing → preimpregnation → washing → activation → washing → surface catalysis → washing → copper facing → washing → nickel plating → washing → nickel envelope → washing → chromium plating → washing → oven dry
Described degreasing is to clean the plastic rubber substrate surface with degreasing fluid, and described degreasing fluid is the CRP CLEANER that the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces, and described to remove oil temperature can be 50 ℃, and the time of oil removing was generally 5 minutes.
Described surface adjustment is described plastic rubber substrate to be adjusted in the liquid on 50 ℃ surface flooded 1 fen, and it is the aqueous solution that liquid is adjusted on described surface, contains the sulfuric acid of 20ml/L, the surfactant of 3ml/L (the CRP UNIPLA that the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces).
Described alligatoring is that described plastic rubber substrate was flooded 5 fens in 65 ℃ coarsening solution, described coarsening solution is the aqueous solution, contains the sulfuric acid, 0.4 milliliter of chromic anhydride, the 380g/L of 380g/L/the rise trivalent chromic ion of additive (the CRP alligatoring additive that the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces), 5g/L.
Described neutralization is to flood 30 seconds in 20 ℃ neutralizer through the plastic rubber substrate after the alligatoring, and described neutralizer is the aqueous solution, contains the CRP NEUTRALIZER 300 (the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces) of 10mL/L, and the pH value of described neutralizer is 10.
Described preimpregnation is to flood 10 seconds in 15 ℃ presoak through the plastic rubber substrate after the neutralisation treatment, and described presoak is the aqueous solution, contains the 35 volume % hydrochloric acid of 150mL/L.
Described activation is that the plastic rubber substrate through preimpregnation was flooded 5 minutes in 10 ℃ activating solution, and described activating solution is the aqueous solution, contains the PdCl of 0.5g/L
2, 30mL/L 35 volume %HCl.
Described surface catalysis is that described plastic rubber substrate was flooded 4 minutes in catalytic liquid under 30 ℃.Described catalytic liquid is the aqueous solution, contains the catalyst (the CRP CATALYST K that the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces) of 25mL/L, the palladium ion of 170mg/L, the additive (the CRP CATALYST additive that the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces) of 20mL/L and the 35 volume % hydrochloric acid of 200mL/L.
Described copper facing be with through this plastic rubber substrate behind the surface catalysis as negative electrode, be anode with the stainless steel, in electroplate liquid, electroplate, described electroplate liquid is an acid copper plating solution, the temperature of described plating is 10 ℃, current density is 2A/dm
2, the time of plating is 10 minutes.Described acid copper plating solution is the aqueous solution, contains the copper sulphate of 180g/L, the sulfuric acid of 30g/L, the chlorion of 50mg/L, the COPPERMU (the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces) of 3mL/L and the COPPER A (the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces) of 0.3mL/L.The thickness of the copper layer that forms is 5 microns.
Described nickel plating is to be negative electrode with the plastic rubber substrate that is formed with the copper layer, is anode with the stainless steel, electroplates in electroplate liquid, and described electroplate liquid is a nickel plating bath, and the temperature of described plating is 30 ℃, and current density is 2A/dm
2, the time of plating is 10 minutes.Described nickel plating bath is the aqueous solution, contains nickelous sulfate, the nickel chloride of 50g/L, the boric acid of 40g/L, the 0.2mL/L additive (the ACNA HSB that the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces) of 250g/L, and the pH value of described nickel plating bath is 4.4.
Described nickel envelope is after carrying out above-mentioned nickel plating, is negative electrode with the plastic rubber substrate, is anode with the stainless steel, electroplates in electroplate liquid, and described electroplate liquid is the nickel sealing liquid, and the temperature of described plating is 40 ℃, and current density is 0.5A/dm
2, the time of plating is 1 minute.Described nickel envelope plating bath is the aqueous solution, contain the nickelous sulfate of 200g/L, the nickel chloride of 50g/L, the boric acid of 40g/L, the nickel envelope powder (Ni-351D that the Jieyang produces than lattice Lay chemical industry Co., Ltd) of 15g/L, the additive (the SMPC SERIES that the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces) of 0.2mL/L, the pH value of described nickel sealing liquid is 4.4.The thickness of the final nickel dam that forms is 10 microns.
Described chromium plating is to be negative electrode with the plastic rubber substrate that is formed with copper layer and nickel dam, is anode with the stainless steel, electroplates in electroplate liquid, and described electroplate liquid is the chromium plating bath, and the temperature of described plating is 40 ℃, and current density is 20A/dm
2, the time of plating is 5 minutes.Described chromium plating bath is the aqueous solution, contains the chromic anhydride of 230g/L, the sulfuric acid of 2.2g/L, the trivalent chromic ion of 3g/L, the fog inhibitor (the RM-118 X of auspicious phase fine chemistry Engineering Co., Ltd production) of 0.03mL/L.The thickness of the chromium layer that forms is 10 microns.
Described washing is with 500 milliliters deionized water rinsing 2 times with plastic rubber substrate.
Described drying is with plastic rubber substrate in 50 ℃ baking oven dry 15 minutes.
It is 2 * 10 that the plastic rubber substrate that will be formed with the chromium layer places vacuum
-2In the vacuum chamber of handkerchief, carry out radio frequency with oxygen and clean, the power of described radio frequency is 600 watts, and the time of described cleaning is 2 minutes; Then 2 * 10
-3Under the vacuum of handkerchief, feeding is as the inert gas of working gas, feed nitrogen simultaneously as reacting gas, this inert gas is ionized the back and under electric field action the titanium as target is carried out vacuum sputtering, the reaction of the titanium of described vacuum sputtering and reacting gas generates titanium nitride, and deposits on the described plastic rubber substrate and form ceramic layer; The power of described vacuum sputtering is 8.5 kilowatts, and the distance of described target and plastic rubber substrate is 10 centimetres, and the time of vacuum sputtering is 4 minutes.The thickness of the ceramic layer that forms is 0.2 micron.
The above-mentioned plasthetics that obtains has the texture of pottery, good hand touch.This plasthetics is carried out anti-wear performance and film adhesion test, and concrete grammar is as follows, and the result is as shown in table 1.
1) wearability test:
With RCA paper tape wear resistant instrument F350001, (the TOKYO HI MAX 11/16inch of society * 330m) measures the rete anti-wear performance to WIDEPAPER in 25 ℃, the environment of relative humidity 40%.Test according to following setting: load 175 grams, rotating speed 15 circles/minute, every paper tape loop length is 16 centimetres, test 350 circles.Whether observe the plasthetics surface after test finishes has base material to expose.
2) adhesive force test:
Draw lattice with hundred lattice cuttves (Erichsen Cross Hatch Cutter Model 295) on the plasthetics surface, cut is deeply to base material, come the backwash sample surfaces repeatedly with soft brush, then the 3M600 adhesive tape is adhered to the plasthetics surface, place after 5 minutes, uncover in the time of second at 0.5-1 with the angle of 60 degree.Examine under a microscope plasthetics surface then and judge the adhesive force rank of plasthetics rete according to following description, wherein the acceptable rank is 0 grade or 1 grade.The result is as shown in table 1.
0 grade: do not have grid to come off.
1 grade: the area that grid comes off is less than 5%.
2 grades: the area that grid comes off is more than or equal to 5%, but less than 15%.
3 grades: the area that grid comes off is more than or equal to 15%, but less than 35%.
4 grades: grid comes off area more than or equal to 35%, but less than 65%.
5 grades: grid comes off area more than or equal to 65%.
Embodiment 2
Present embodiment illustrates plasthetics of the present invention and preparation method thereof.
To electroplate level acrylonitrile-butadiene-styrene (the ABS MP-211 of LG) and, carry out injection mo(u)lding, obtain plastic rubber substrate with injection moulding machine as raw material.
This plastic rubber substrate is handled according to following operation successively:
Degreasing → washing → surface adjustment → washing → alligatoring → washing → neutralization → washing → preimpregnation → washing → activation → washing → surface catalysis → washing → copper facing → washing → nickel plating → washing → nickel envelope → washing → chromium plating → washing → oven dry
Described degreasing is to clean the plastic rubber substrate surface with degreasing fluid, and described degreasing fluid is the CRP CLEANER that the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces, and described to remove oil temperature can be 80 ℃, and the time of oil removing was generally 12 minutes.
Described surface adjustment is described plastic rubber substrate to be adjusted in the liquid on 50 ℃ surface flooded 5 fens, it is the aqueous solution that liquid is adjusted on described surface, contains the sulfuric acid of 40ml/L, the surfactant of 20ml/L (the CRP UNIPLA that the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces).
Described alligatoring is that described plastic rubber substrate was flooded 10 fens in 70 ℃ coarsening solution, described coarsening solution is the aqueous solution, contains the sulfuric acid, 1.4 milliliters of chromic anhydride, the 450g/L of 420g/L/the rise trivalent chromic ion of additive (the CRP alligatoring additive that the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces), 25g/L.
Described neutralization is to flood 80 seconds in 30 ℃ neutralizer through the plastic rubber substrate after the alligatoring, and described neutralizer is the aqueous solution, contains the CRP NEUTRALIZER 300 (the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces) of 30mL/L, and the pH value of described neutralizer is 12.
Described preimpregnation is to flood 60 seconds in 30 ℃ presoak through the plastic rubber substrate after the neutralisation treatment, and described presoak is the aqueous solution, contains the 35 volume % hydrochloric acid of 250mL/L.
Described activation is that the plastic rubber substrate through preimpregnation was flooded 25 minutes in 30 ℃ activating solution, and described activating solution is the aqueous solution, contains the PdCl of 1.0g/L
2, 40mL/L 35 volume %HCl.
Described surface catalysis is that described plastic rubber substrate was flooded 8 minutes in catalytic liquid under 30 ℃.Described catalytic liquid is the aqueous solution, contains the catalyst (the CRP CATALYST K that the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces) of 40mL/L, the palladium ion of 270mg/L, the additive (the CRP CATALYST additive that the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces) of 100mL/L and the 35 volume % hydrochloric acid of 270mL/L.
Described copper facing be with through this plastic rubber substrate behind the surface catalysis as negative electrode, be anode with the stainless steel, in electroplate liquid, electroplate, described electroplate liquid is an acid copper plating solution, the temperature of described plating is 35 ℃, current density is 8A/dm
2, the time of plating is 30 minutes.Described acid copper plating solution is the aqueous solution, contains the copper sulphate of 200g/L, the sulfuric acid of 60g/L, the chlorion of 80mg/L, the COPPERMU (the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces) of 6mL/L and the COPPER A (the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces) of 0.7mL/L.The thickness of the copper layer that forms is 15 microns.
Described nickel plating is to be negative electrode with the plastic rubber substrate that is formed with the copper layer, is anode with the stainless steel, electroplates in electroplate liquid, and described electroplate liquid is a nickel plating bath, and the temperature of described plating is 50 ℃, and current density is 8A/dm
2, the time of plating is 13 minutes.Described nickel plating bath is the aqueous solution, contains nickelous sulfate, the nickel chloride of 60g/L, the boric acid of 50g/L, the 0.8mL/L additive (the ACNA HSB that the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces) of 300g/L, and the pH value of described nickel plating bath is 3.8.
Described nickel envelope is after carrying out above-mentioned nickel plating, is negative electrode with the plastic rubber substrate, is anode with the stainless steel, electroplates in electroplate liquid, and described electroplate liquid is the nickel sealing liquid, and the temperature of described plating is 60 ℃, and current density is 2.5A/dm
2, the time of plating is 2.5 minutes.Described nickel envelope plating bath is the aqueous solution, contain the nickelous sulfate of 250g/L, the nickel chloride of 90g/L, the boric acid of 45g/L, the nickel envelope powder (the Ni-351D nickel envelope powder that the Jieyang produces than lattice Lay chemical industry Co., Ltd) of 20g/L, the additive (the SMPC SERIES that the difficult to understand wild Scientific and Technical Industry Co., Ltd in Hangzhou produces) of 1.0mL/L, the pH value of described nickel sealing liquid is 3.9.The thickness of the final nickel dam that forms is 25 microns.
Described chromium plating is to be negative electrode with the plastic rubber substrate that is formed with copper layer and nickel dam, is anode with the stainless steel, electroplates in electroplate liquid, and described electroplate liquid is the chromium plating bath, and the temperature of described plating is 60 ℃, and current density is 35A/dm
2, the time of plating is 13 minutes.Described chromium plating bath is the aqueous solution, contains the chromic anhydride of 270g/L, the sulfuric acid of 2.9g/L, the trivalent chromic ion of 6g/L, the fog inhibitor (RM-118X of auspicious phase fine chemistry Engineering Co., Ltd production) of 0.05mL/L.The thickness of the chromium layer that forms is 28 microns.
Described washing is with 500 milliliters deionized water rinsing 2 times with plastic rubber substrate.
Described drying is with plastic rubber substrate in 50 ℃ baking oven dry 15 minutes.
It is 2 * 10 that the plastic rubber substrate that will be formed with the chromium layer places vacuum
-2In the vacuum chamber of handkerchief, carry out radio frequency with oxygen and clean, the power of described radio frequency is 900 watts, and the time of described cleaning is 5 minutes; Then 4 * 10
-3Under the vacuum of handkerchief, feeding is as the argon gas of working gas, feed acetylene simultaneously as reacting gas, this inert gas is ionized the back and under electric field action the titanium as target is carried out vacuum sputtering, the reaction of the titanium of described vacuum sputtering and reacting gas generates titanium carbide, and deposits on the described plastic rubber substrate and form ceramic layer; The power of described vacuum sputtering is 9.5 kilowatts, and the distance of described target and plastic rubber substrate is 15 centimetres, and the time of vacuum sputtering is 10 minutes.The thickness of the ceramic layer that forms is 1 micron.
The above-mentioned plasthetics that obtains has the texture of pottery, good hand touch.Method according to embodiment 1 is carried out anti-wear performance and film adhesion test to this plasthetics, and the result is as shown in table 1.
Embodiment 3
Method according to embodiment 1 prepares plasthetics, and different is, it is 2 * 10 that the plastic rubber substrate that will be formed with the chromium layer places vacuum
-2In the vacuum chamber of handkerchief, carry out radio frequency with oxygen and clean, the power of described radio frequency is 900 watts, and the time of described cleaning is 5 minutes; Then 4 * 10
-3Under the vacuum of handkerchief, feeding is as the argon gas of working gas, feed acetylene and nitrogen simultaneously as reacting gas, this argon gas is ionized the back and under electric field action the titanium as target is carried out vacuum sputtering, the titanium of described vacuum sputtering and reacting gas reaction generate titanium carbonitride, and deposit to formation titanium carbonitride ceramic layer on the described plastic rubber substrate; The power of described vacuum sputtering is 9.5 kilowatts, and the distance of described target and plastic rubber substrate is 10 centimetres, and the time of vacuum sputtering is 8 minutes.The thickness of the ceramic layer that forms is 0.5 micron.
The above-mentioned plasthetics that obtains has the texture of pottery, good hand touch.Method according to embodiment 1 is carried out anti-wear performance and film adhesion test to this plasthetics, and the result is as shown in table 1.
Embodiment 4
Method according to embodiment 1 prepares plasthetics, and different is, it is 2 * 10 that the plastic rubber substrate that will be formed with the chromium layer places vacuum
-2In the vacuum chamber of handkerchief, carry out radio frequency with oxygen and clean, the power of described radio frequency is 900 watts, and the time of described cleaning is 5 minutes; Then 4 * 10
-3Under the vacuum of handkerchief, feeding is as the argon gas of working gas, feed acetylene simultaneously as reacting gas, this argon gas is ionized the back and under electric field action the titanium as target is carried out vacuum sputtering, the titanium of described vacuum sputtering and reacting gas reaction generate titanium carbide, and deposit to formation titanium carbide ceramic layer on the described plastic rubber substrate; The power of described vacuum sputtering is 9.5 kilowatts, and the distance of described target and plastic rubber substrate is 10 centimetres, and the time of vacuum sputtering is 2 minutes.And then plastic rubber substrate is placed vacuum is 4 * 10
-3In the vacuum chamber of handkerchief, feeding is as the argon gas of working gas, feed nitrogen simultaneously as reacting gas, this argon gas is ionized the back and under electric field action the titanium as target is carried out vacuum sputtering, the titanium of described vacuum sputtering and reacting gas reaction generate titanium nitride, and deposit to formation titanium nitride ceramic layer on the described plastic rubber substrate; The power of described vacuum sputtering is 9.5 kilowatts, and the distance of described target and plastic rubber substrate is 10 centimetres, and the time of vacuum sputtering is 2 minutes.Finally, the thickness of total ceramic layer is 0.4 micron.
The above-mentioned plasthetics that obtains has the texture of pottery, good hand touch.Method according to embodiment 1 is carried out anti-wear performance and film adhesion test to this plasthetics, and the result is as shown in table 1.
Table 1
| The embodiment numbering | Anti-wear performance | Adhesive force |
| Embodiment 1 | Do not see behind 350 circles that base material is exposed | 0 grade |
| Embodiment 2 | Do not see behind 350 circles that base material is exposed | 0 grade |
| Embodiment 3 | Do not see behind 350 circles that base material is exposed | 0 grade |
| Embodiment 4 | Do not see behind 350 circles that nickel dam is exposed | 0 grade |
As can be seen from Table 1, the high abrasion resistance of the plasthetics that embodiment of the invention 1-4 makes, and also the rete that the plasthetics surface forms has good adhesive force.
Claims (9)
1, a kind of plasthetics, these goods comprise plastic rubber substrate, it is characterized in that these goods outwards also comprise copper layer, nickel dam, chromium layer and ceramic layer successively from the plastic rubber substrate surface, one deck in titanium nitride layer, titanium carbide layer and the titanium carbonitride layer or which floor described ceramic layer be.
2, goods according to claim 1, wherein, the thickness of described copper layer is the 5-15 micron, and the thickness of nickel dam is the 5-30 micron, and the thickness of described chromium layer is the 5-30 micron, and the thickness of described ceramic layer is the 0.1-2 micron.
3, goods according to claim 1, wherein, described plastic rubber substrate is for electroplating the level plastic rubber substrate.
4, the preparation method of the described plasthetics of claim 1, it is characterized in that, this method is included in the plastic rubber substrate surface and forms copper layer, nickel dam and chromium layer successively, forms ceramic layer then on the chromium layer, and one deck in titanium nitride layer, titanium carbide layer and the titanium carbonitride layer or which floor described ceramic layer be.
5, method according to claim 4, wherein, described copper layer, nickel dam and chromium layer form by electroplating, and it is the 5-15 micron that the condition of described plating makes the thickness of the copper layer of formation, and the thickness of nickel dam is the 5-30 micron, and the thickness of chromium layer is the 5-30 micron.
6, method according to claim 5, wherein, the condition of described electro-coppering comprises that the plastic rubber substrate with conduction is a negative electrode, with copper or insoluble conductor is anode, in electroplate liquid, electroplate, described electroplate liquid is an acid copper plating solution, and the temperature of described plating is 5-40 ℃, and current density is 0.5-8A/dm
2, the time of plating is 10-30 minute; The method of described electronickelling comprises that with the plastic rubber substrate that is formed with the copper layer be negative electrode, is anode with nickel or insoluble conductor, electroplates in electroplate liquid, and described electroplate liquid is a nickel plating bath, and the temperature of described plating is 30-55 ℃, and current density is 2-10A/dm
2, the time of plating is 5-15 minute; The method of described electrodeposited chromium comprises that with the plastic rubber substrate that is formed with copper layer and nickel dam be negative electrode, is anode with chromium or insoluble conductor, electroplates in electroplate liquid, and described electroplate liquid is the chromium plating bath, and the temperature of described plating is 40-60 ℃, and current density is 20-35A/dm
2, the time of plating is 5-15 minute.
7, method according to claim 4, wherein, the method that forms described ceramic layer is a vacuum sputtering plating method, it is the 0.1-2 micron that the condition of described vacuum sputtering plating makes the thickness of described ceramic layer.
8, method according to claim 7, wherein, described vacuum sputtering plating comprises with inert gas as working gas, with nitrogen and/or acetylene as reacting gas, make titanium as target become titanium nitride and/or titanium carbide with nitrogen and/or acetylene reaction and be deposited on the chromium layer of plastic rubber substrate and form ceramic layer, the power of described vacuum sputtering is 8.5-9.5 kilowatt, and the distance of described target and plastic rubber substrate is 5-10 centimetre, and the time of vacuum sputtering is 4-10 minute.
9, method according to claim 4, wherein, described plastic rubber substrate is for electroplating the level plastic rubber substrate.
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| CNA2007101517922A CN101396890A (en) | 2007-09-29 | 2007-09-29 | Plastics products and preparation method thereof |
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| CNA2007101517922A CN101396890A (en) | 2007-09-29 | 2007-09-29 | Plastics products and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103741183A (en) * | 2014-01-16 | 2014-04-23 | 惠州建邦精密塑胶有限公司 | Production process for high-strength and temperature-change-resistant nylon electroplated product |
| CN103935075A (en) * | 2013-01-23 | 2014-07-23 | 深圳富泰宏精密工业有限公司 | Shell and manufacturing method thereof |
| CN105543915A (en) * | 2015-12-25 | 2016-05-04 | 东莞星晖真空镀膜塑胶制品有限公司 | Imitation gold electroplating process for plastic surface |
| CN114466534A (en) * | 2020-11-10 | 2022-05-10 | Oppo广东移动通信有限公司 | Shell of electronic equipment, preparation method of shell and electronic equipment |
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2007
- 2007-09-29 CN CNA2007101517922A patent/CN101396890A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103935075A (en) * | 2013-01-23 | 2014-07-23 | 深圳富泰宏精密工业有限公司 | Shell and manufacturing method thereof |
| CN103935075B (en) * | 2013-01-23 | 2018-07-03 | 深圳富泰宏精密工业有限公司 | Housing and preparation method thereof |
| CN103741183A (en) * | 2014-01-16 | 2014-04-23 | 惠州建邦精密塑胶有限公司 | Production process for high-strength and temperature-change-resistant nylon electroplated product |
| CN105543915A (en) * | 2015-12-25 | 2016-05-04 | 东莞星晖真空镀膜塑胶制品有限公司 | Imitation gold electroplating process for plastic surface |
| CN114466534A (en) * | 2020-11-10 | 2022-05-10 | Oppo广东移动通信有限公司 | Shell of electronic equipment, preparation method of shell and electronic equipment |
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