CN104364421A

CN104364421A - Process for metallizing nonconductive plastic surfaces

Info

Publication number: CN104364421A
Application number: CN201380029727.6A
Authority: CN
Inventors: L.纳鲁斯克维丘斯; D.布迪洛夫斯基斯; O.吉利内; L.塔马索斯凯特塔马休奈特
Original assignee: Atotech Deutschland GmbH and Co KG
Current assignee: Atotech Deutschland GmbH and Co KG
Priority date: 2012-06-05
Filing date: 2013-06-05
Publication date: 2015-02-18
Anticipated expiration: 2033-06-05
Also published as: BR112014029353B1; JP6180518B2; PT2855731E; JP2015518924A; PL2855731T3; US20150129540A1; KR20150024327A; LT5997B; BR112014029353A2; EP2855731B1; ES2575001T3; CA2875323A1; EP2855731A1; CA2875323C; KR102130947B1; CN104364421B; LT2012042A; WO2013182590A1

Abstract

The present invention relates to a process for metallizing nonconductive plastics using an etching solution free of hexavalent chromium. The etching solution is based on a sulphuric acidic solution containing a source of chlorate ions. After the treatment of the plastics with the etching solution, the plastics are metallized by means of known processes.

Description

Make the method for nonconductive plastic material surface metalation

Invention field

The present invention relates to pre-treatment nonconductive plastic material surface before metallization, and can be applicable to the difference industry wherein needing the ornamental of plastic components or functional metal coating.Pre-treatment is carried out in not chromyl solution.

background of invention

Before electroless metallising (mainly electroless nickel plating or copper facing), the ordinary method on pre-treatment nonconductive plastic material surface is made up of following: etched surfaces in chromyl solution, activate in the ion or colloidal solution of palladium compound subsequently, and reduce (in most of the cases) in sodium hypophosphite solution or accelerate (being adsorbed on respectively on frosting) in the acid solution (usual hydrochloric acid) of palladium ion or colloidal palladium particle.

In order to hydrophilization, need during pre-treatment step, etch nonconductive matrix surface, to make surface become hydrophilic in aqueous in other stage of method, adsorb the palladium salt of q.s simultaneously, and ensure that metal plating is suitably attached to nonconductive plastic material surface.In order to cause metal electroless deposition on plastics, activate, reduction subsequently or acceleration.Subsequently, carry out using metal electroless by autocatalytic reaction in metallization solution, the metal wherein deposited from the teeth outwards is as the catalyzer deposited further.This electroless mainly uses metallic nickel and copper.

Subsequently, electrolysis or electrochemical plating can be carried out on the first metal layer.Various metal can be applied, such as other alloy of chromium, nickel, copper and brass or aforementioned metal.

The main drawback of ordinary method relates to the carinogenicity of chromic acid in etching solution.In addition, the metal deposited during electroless deposition step, such as nickel, the also part of support that insulate with plastisol of covering, this causes the metal loss at the solution of electrochemical metal plating subsequently, therefore undesirable.

The various methods overcoming this problem have been proposed in the prior art.

U.S. Patent Application No. 2005/0199587 A1 discloses a kind of method etching nonconductive plastic material surface in acidic solution comprising 20-70g/l potassium permanganate.More than mention the best KMnO in solution ₄concentration is close to 50g/l.When concentration is lower than 20g/l, solution is invalid, and upper limit of concentration is determined by the solubleness of potassium permanganate.After etching, activate in the palladium salts solution comprising amine, and such as further reduction treatment in hydroborate, hypophosphite or hydrazine solution.

But this method has remarkable shortcoming.(advise about 50g/l, with 48% volume phosphoric acid) under permanganate concentration high in the etch solution, it decomposes very soon, especially at high temperature.Suggestion temperature is 100 ℉, namely 37 DEG C.Test shows, and in this temperature, solution became invalid after 4 to 6 hours, that is, frosting not hydrophilization, and some local maintenance is not plated during metallizing, very weak with the sticking power of plastics in plating zones.Need to carry out regulator solution through conventional new peak manganate part, permanganate is not cheap.In addition, also generate insoluble permanganate degradation production, pollute just on metallized surface.

In addition, when with etch reaction products plating and Manganse Dioxide, the etching in permanganate solution makes the plastisol insulator surface of support activate.The latter promotes that palladium compound is adsorbed on plastisol, and this tends in electroless metal deposition GOLD FROM PLATING SOLUTION genusization.Generate the feature that Manganse Dioxide is the permanganate etch solution of any composition from the teeth outwards.Therefore, very important object of the present invention avoids backbone metal, and avoid the metal loss at metalization level subsequently.

Lithuania number of patent application LT 2008-082 also relates to pre-treatment nonconductive plastic material surface before metallization.A kind of pretreatment compositions is wherein disclosed, utilize the temperature of 10-80 DEG C, in the sulfuric acid of 13mol/L (about 75% volume)-17mol/L (about 90% volume) concentration 0,005-0,2M oxidizing agent solution etches such as polyimide 1-2 minute, and wherein oxygenant can be KMnO ₄, HClO ₄, V ₂o ₅, KClO ₃.At chlorate anions (ClO ₃ ^-, M=83.5g/mol) when, this is equivalent to the concentration of 0.4 – 16.7g/l.

In the table 2 of this application, provide an example, example comprises 7mol/L (about 50% volume) sulfuric acid and 0.2mol/L (16.7g/L) chlorate anions.But the chlorate anions having shown high density like this causes preprocessing solution fast decoupled, and this is undesirable.

invention describes

Therefore, the present invention is based on following problem: the metallization also failing to realize by environmental safety mode the goods be made up of nonconductive plastic material so far, and have enough reliability of technology and the metal level adhesion strength used subsequently is enough.

Therefore, the object of the invention is to find that these are nontoxic for the etching solution on the nonconductive plastic material surface of pre-treatment preparations, but provide enough adhesion strengths for the metal level that frosting is used.

This purpose is by following realization: be used in the application in 50-80% volume sulfuric acid and comprise the solvable oxymuriate of 0.2 to 15.0g/l (based on KClO ₃m=122.55, i.e. 0.0016mol/l to 0.12mol/l) etching solution etching frosting as the treatment process of frosting before electroless metallising, treatment process is made up of following: apparatus has the inorganic acid solution etching plastics of oxygenant, activated by palladium salts solution, and by reducing or accelerating solution-treated.Etching is preferably carried out in room temperature (15-28 DEG C, preferred 20-25 DEG C), but also can carry out at the higher temperature up to 40 DEG C or 50 DEG C, and condition is that the stability of solution is controlled.Preprocessing solution optionally can comprise the another kind of oxygenant up to 20g/l, and it has the standard oxidation potential exceeding chlorate anions.

Etching period with body material and alteration of form thereof, and is determined by routine test.General between 1 and 20 minute, preferably no longer than 10 minutes.

Chloranion source can be any water-soluble salt.The most often use sodium chlorate and Potcrate.

In etching solution, the concentration of chloranion is 0.0016mol/l to 0.12mol/l, or preferably up to 0.03mol/l or even more preferably up to 0.04mol/l.Preferred scope between 0.003mol/l and 0.08mol/l, or between 0.01mol/l and 0.06mol/l or between 0.004mol/l and 0.04mol/l.

The concentration of sulfuric acid between 50% volume and 80% volume, preferably between 55% volume and 70% volume, even more preferably between 60% volume and 65% volume.

Optionally can comprise phosphoric acid in the etch solution as other acid.The concentration of phosphoric acid is generally 10% volume to 40% volume, preferably between 15% volume and 25% volume or 30% volume.When using phosphoric acid in addition, the sticking power of metal plating layer unexpectedly can be improved in addition.

Between 60% volume and 65% volume sulfuric acid and between 20% volume and 30% volume phosphoric acid mixture particularly preferably.

Before electroless metallising, the method on pretreated plastic surface comprises, plastics are etched in the inorganic acid solution being added with oxygenant, activate in palladium salts solution, and process in reduction or acceleration solution, it is characterized in that 0.02 – 15.0g/l soluble chlorine hydrochlorate (such as in room temperature is by 50-80% volume sulfuric acid, 0.5 – 5g/l soluble chlorine hydrochlorate) solution etches frosting, and process in addition in alkali hydroxide soln, then activated and use reduction/acceleration solution-treated by palladium compound solution.

Etching solution optionally can comprise the another kind of oxygenant of 2 to 20g/l, and it has the standard oxidation potential exceeding chloranion.

Alkaline metal chlorate and sulfuric acid generate yellow compound, and it is at H ₂sO ₄standard oxidation potential in solution medium is enough to react in room temperature and frosting.Due to this reaction, frosting becomes hydrophilic, and with sufficient intensity absorption palladium compound.Yellow reaction product between oxymuriate and sulfuric acid is the poisonous substance of palladium catalyst.At etching, it penetrates the plastisol insulator surface layer of support, and stop in electroless metallising solution on plastisol electroless deposition of metals, the metallization processes occurred on the surface at nonconductive plastic material is unaffected.

At 1 to 2g/l sodium chlorate or Potcrate and 5 to 10g/l second strong oxidizer (such as NaBiO ₃) dissolve time, etching property keeps a couple of days in room temperature, and can use solution under not regulating.If only comprise sodium chlorate/Potcrate in the solution, etching property keeps the time (the longest 24 hours) of much shorter.

Its important difference feature being different from the proposed method of permanganate etch is made to be between coating and plastics, obtain very high adhesion value, usually more than 1.2 to 1.3kg/cm.Except the composition of etching solution and etching period (having the optimal etch time to each composition), these values also depend on the composition of activated solution.Usually, when using actual activated solution, the adhesion value obtained is higher than those values obtained with colloidal activating solution.

Etching solution can be prepared as follows:

The 700ml vitriol oil is mixed with 300ml deionized water.Solution is cooled.Then 2g Potcrate and 10g sodium perchlorate is made to be dissolved in solution.Solution is ready to use.The the second oxygenant sodium perchlorate being better than Repone K is optional.Its increases the time limit of service of composition, but does not need it to obtain the well attached of metal plating layer subsequently.

When the amount preparing solution water used compares more than 50% volume with sulfuric acid, between chloranion and sulfuric acid molecule, do not generate yellow plastic oxygenated compound, therefore, the water-content of solution preferably should more than 50% volume.

The amount preparing solution water used to compare with sulfuric acid be less than 20% volume time, because sulfuric acid concentration is too high, decompose at etching frosting, therefore, between chemical nickel coating and plastics, there is no sticking power.

If the amount being dissolved in the Potcrate of solution is less than 0.5g/l, etching process is consuming time is longer than 15 minutes, and therefore, this concentration is unacceptable.

If be dissolved in the amount of the Potcrate of solution more than 5.0g/l, then after minimum etching period (namely 2 to 3 minutes), can be observed over etching, this produces much weak adhesion strength, and therefore, this high concentration cl hydrochlorate is also unacceptable.But according to body material, the higher concentration producing the highest 15g/l of enough sticking power also can accept.

Object of the present invention realizes further by following methods of the present invention:

Make the method for the nonconductive plastic material surface metalation of goods, described method comprises following methods step:

A) with the above-mentioned etching solution etching frosting comprising chloranion source, described chloranion source obtains 0.0016 to 0.12mol/l chloranion concentration in 50-80% volume sulfuric acid;

B) with the solution-treated frosting of metallic colloid or metallic compound, described metal is selected from the metal of periodic table of elements I transition group and periodic table of elements VIII transition group; And

C) metallization of plastic surface is made with metallization solution;

Should be appreciated that, in the context of the present invention, goods refer to the goods be made up or used at least one deck at least one nonconductive plastic material of at least one nonconductive plastic material and cover.Therefore, goods have the surface of at least one nonconductive plastic material.Should be appreciated that, in the context of the present invention, frosting mean goods these described in surface.

Method steps of the present invention carries out with regulation order, but need not with immediately order.Can other method steps be carried out, and cleaning step can be carried out in addition in all cases between the steps, preferably use water.

Frosting is made up of at least one nonconductive plastic material.In one embodiment of the invention, at least one nonconductive plastic material is selected from the mixture of acrylonitrile-butadiene-styrene copolymer (Acrylonitrile Butadiene—Styrene copolymer), polymeric amide (PA), polycarbonate (PC) and Acrylonitrile Butadiene—Styrene copolymer and other polymkeric substance of at least one.

In a preferred embodiment of the invention, nonconductive plastic material is the mixture of Acrylonitrile Butadiene—Styrene copolymer or Acrylonitrile Butadiene—Styrene copolymer and other polymkeric substance of at least one.Other polymkeric substance of at least one is more preferably polycarbonate (PC), and this represents particularly preferably ABS/PC mixture.

Etching solution of the present invention is not preferably containing any chromium or chromium cpd, and etching solution, neither containing chromium (III) ion, does not also contain chromium (VI) ion.Therefore, etching solution of the present invention is not containing chromium or chromium cpd, and etching solution is not containing chromium (III) ion and chromium (VI) ion.

In another preferred embodiment of the present invention, at method steps A) and B) between carry out following other method steps:

A i) in the solution comprising basic solution, process frosting.

Other method steps A i) be also referred to as neutralizing treatment.Can use any alkaline source, the aqueous solution of sodium hydroxide is preferred.

Of the present invention another for selecting in embodiment, at method steps A) and B) between carry out following other method steps:

A i) process frosting comprising in the solution for the reductive agent of chloranion and the second optional oxygenant.

Other method steps A i) be also referred to as reduction treatment.This reduction treatment minimizing is attached to the chloranion of frosting and the second optional oxygenant, and promotes to remove these ions.Reductive agent is such as selected from hydroxylammonium sulfate, hydroxylammonium chloride and hydrogen peroxide.

Method of the present invention comprises method steps B further), the wherein solution-treated of frosting metallic colloid or metallic compound.

The metal of metallic colloid or metallic compound is selected from the metal of the periodic table of elements (PTE) I transition group and PTE VIII transition group.

The metal of PTE VIII transition group is selected from the mixture of palladium, platinum, iridium, rhodium and two or more these metals.The metal of PTE I transition group is selected from the mixture of gold and silver and these metals.

Preferable alloy in metallic colloid is palladium.Metallic colloid protective colloid-stabilisedization.Protective colloid is selected from metal protection colloid, organic protective colloid and other protective colloid.Preferably use tin ion as metal protection colloid.Organic protective colloid is selected from polyvinyl alcohol, polyvinylpyrrolidone and gelatin, preferably polyethylene alcohol.

In a preferred embodiment of the invention, method steps B) in the solution of metallic colloid be the activator solution with palladium/tin colloid.This colloidal solution obtains from palladium salt, tin (II) salt and mineral acid.Preferred palladium salt is Palladous chloride.Preferred tin (II) salt is tin chloride (II).Mineral acid can be made up of hydrochloric acid or sulfuric acid, preferred hydrochloric acid.Colloidal solution is by making Palladous chloride be reduced into palladium to generate by tin chloride (II).It is completely that Palladous chloride changes into colloid, and therefore, colloidal solution is no longer containing any Palladous chloride.The concentration of palladium is based on Pd ²⁺for 5mg/l-100mg/l, preferred 20mg/l-50mg/l, more preferably 30mg/l-45mg/l.The concentration of tin chloride (II) is based on Sn ²⁺for 0.5g/l-10g/l, preferred 1g/l-5g/l, more preferably 2g/l-4g/l.The concentration of hydrochloric acid is 100ml/l – 300ml/l (37% weight HCl).In addition, palladium/tin colloid solution also comprises tin (IV) ion, and tin (IV) ion is generated by tin (II) ionic oxide formation.At method steps B) period colloidal solution temperature be 20 DEG C-50 DEG C, preferably 35 DEG C-45 DEG C.Utilize the treatment time of activator solution for 0.5min-10min, preferred 2min-5min, more preferably 3min-5min.

In another embodiment of the invention, at method steps B) in, replace metallic colloid with the solution of metallic compound.The solution of metallic compound used is the solution comprising acid and metal-salt.Metal in metal-salt is made up of the metal of one or more above listed PTE I and VIII transition group.Metal-salt can be palladium salt, preferred Palladous chloride, palladous sulfate or acid chloride, or silver salt, preferred silver acetate.Acid is preferably hydrochloric acid.Or, also can use metal complex, such as palladium complex salt, such as palladium-aminopyridine complex salts.Method steps B) in metallic compound exist with the concentration based on metal 40mg/l to 80mg/l.The solution of metallic compound can use, preferably at 25 DEG C 25 DEG C to 70 DEG C temperature.Utilize the treatment time of metal compound solution for 0.5min – 10min, preferred 2min – 6min, more preferably 3min – 5min.

At method steps A) and B) between can carry out following other method steps:

A ii) in acidic aqueous solution, process frosting.

Preferably at method steps A i) and B) between carry out method steps A ii).In the method for the invention, if at method steps A i) protective cradle afterwards, then more preferably at protective cradle and method steps B) between carry out method steps A ii).

At method steps A ii) middle process frosting is also referred to as front dipping, and acidic aqueous solution is used as front dipping solution.Front dipping solution has and method steps B) in the identical composition of colloidal solution, but there is not metal in colloid and protective colloid thereof.At method steps B) in use palladium/tin colloid solution, if colloidal solution comprises hydrochloric acid equally, then before dipping solution exclusively comprise hydrochloric acid.For front dipping, briefly immerse front dipping solution in envrionment temperature just enough.Do not clean frosting, in front dipping solution process after, they are directly used method steps B further) colloidal solution process.

At method steps B) when comprising with colloidal metal solution process frosting, preferably carry out method steps A ii).Also can at method steps B) comprise and carry out method steps A ii with during metal compound solution process frosting).

At method steps B) in after metallic colloid or metallic compound process frosting, can clean it.

In another embodiment of the invention, at method steps B) and C) between carry out following other method steps:

B i) in acidic aqueous solution, process frosting, and

B ii) in metallization solution, make frosting electroless metallising.

Embodiment signal is shown in table 1.

Method steps	Composition	Time	Temperature
				A) etch	Table 2	4-6min	22℃
A i) neutralization	10g/l NaOH	4min	20℃
				A ii) front dipping	Hydrochloric acid, about 10% weight	1min	20℃
B) activate	Palladium/tin colloid in hydrochloric acid soln	3-6min	20-45℃
				B i) accelerate	Sulfuric acid (5%)	2-6min	40-50℃
B ii) electroless metal deposition	Chemical reduction nickel plating or copper facing	6-20min	30-50℃
				C) metal deposition	Such as, Cu electroplating or nickel plating	15-70min	20-35℃

Table 1: plastics metalizing embodiment

Goods will by electroless metallising method metallization time, namely the first metal layer will by being applied to frosting without method for electrically time, the method steps B i utilizing these other) and B ii).

If method steps B) in activation carry out with metallic colloid, then in order to remove the colloid composition such as protective colloid in colloidal solution from frosting, at method steps B i) in accelerator solution process frosting.If at method steps B) in colloid in colloidal solution be palladium/tin colloid, then preferred accelerator solution used is aqueous acid.Such as, acid is selected from sulfuric acid, hydrochloric acid, citric acid and Tetrafluoroboric acid.When palladium/tin colloid, accelerator solution helps to remove the tin compound being used as protective colloid.

Or, at method steps B) in when replacing metallic colloid for activating with the solution of metallic compound, at method steps B i) in carry out reductive agent process.Then, if when the solution of metallic compound is the acidic solution of the hydrochloric acid soln of Palladous chloride or silver salt, the reductant solution used for this purpose comprises hydrochloric acid and tin chloride (II).Reductant solution also can comprise another kind of reductive agent, such as NaH ₂pO ₂or borine or hydroborate, such as basic metal borine or alkaline-earth metal borine or dimethyl amino borane.Preferably in reductant solution, use NaH ₂pO ₂.

At method steps B i) in reductant solution accelerate or process after, first can clean frosting.

At method steps B i) and optional one or more cleaning steps after, carry out method steps B ii), wherein make frosting electroless metallising.Such as, bathed electroless nickel plating with conventional nickel, the bath of described nickel especially comprises single nickel salt, as the hypophosphite (such as, sodium hypophosphite) of reductive agent and organic complexing agent and pH adjusting agent (such as, buffer reagent).Reductive agent used can be similarly the mixture of dimethyl amino borane or hypophosphite and dimethyl amino borane.

Or available bath without electrolytic copper carries out electroless copper, generally comprises mantoquita without electrolytic copper bath, such as, copper sulfate or Hypophosporous Acid, 50 copper; And reductive agent, such as formaldehyde or hypophosphite (such as basic metal or ammonium salt) or Hypophosporous Acid, 50; And one or more other complexing agents, such as tartrate; And pH adjusting agent, such as sodium hydroxide.

Subsequently, in order to obtain functional or decorative surface, the surperficial electrolytic metal chemical that electroconductibility is so provided can be made further.

The step C of method of the present invention) for make metallization of plastic surface with metallization solution.Method steps C) in metallization can electrolysis carry out.For electrolytic metal chemical, available any required metal deposition bath such as nickel deposited, copper, silver, gold, tin, zinc, iron, lead or their alloy.These deposition baths are familiar with by those skilled in the art.The bath of Watts nickel is general is used as the bath of bright nickel, and this bath comprises single nickel salt, nickelous chloride and boric acid, also comprises asccharin as additive.The example of the composition of bathing as bright copper comprises copper sulfate, sulfuric acid, sodium-chlor and organosulfur compound, and wherein sulphur is in low-oxidation-state, and such as organic sulfide or disulphide, as additive.

Method steps C) in the effect of metallization of plastic surface be frosting metal deposition, metal is selected from the above metal enumerated for deposition bath.

In another embodiment of the invention, at method steps C) after carry out following other method steps:

C i) store at elevated temperatures through metallized frosting.

As wherein with metal by the idioelectric all electro-plating methods of wet chemical method plating, after using metal level, the adhesion strength between metal and plastic substrate increased in the first stage.In room temperature, this process completed after about 3 days.This is by storing remarkable acceleration at elevated temperatures.This process completes after about 1 hour at 80 DEG C.Assuming that initial low adhesion strength also stops the thin water layer forming electrostatic force to produce by the interface between metal and non-conductive matrix.

Therefore, method of the present invention can realize the nonconductive plastic material surface metalation of goods with good process reliability and the splendid adhesion strength using metal level subsequently.The adhesion strength being administered to the metal level of frosting reaches up to 2.7N/mm (be similar to and be equivalent to 2.7kg/cm, 1kg/cm=0.98N/mm) or higher value.Therefore, the adhesion strength reached is also far above the intensity reached after can etching frosting (see embodiment 2 and 3) according to prior art chromatosulfuric acid.

In general, industrial application needs the adhesion value being greater than 0.8N/mm, and the object wanting plating non-complex shaping.In general, sedimental sticking power is higher, and stability is better.

In addition, not only flat frosting is metallized with high-adhesion by method of the present invention, and uneven shaping frosting, such as spray header, also provide uniform strong adhesion metal coating.

By method process frosting of the present invention preferably in conventional impregnation methods, immerse solution to carry out by container that goods are processed successively wherein respectively.In the case, goods can be fixed to support or be contained in drum in immerse solution.It is preferred for being fixed to support.Or, by being such as placed on dish, and with horizontal direction continus convergence by equipment, also can in so-called handling equipment treatment articles.

effective embodiment

The effective embodiment of the following stated is intended to explain the present invention.

embodiment 1

According to U.S. Patent Application No. 2005/0199587 A1, comprising 50g/l KMnO ₄45% volume phosphoric acid solution at 37 DEG C in 5min (for ABS) or 15min (for PC/ABS) period, or there is 0.5 to 5.0g/l KClO ₃and to be added with in 50 to 80% volume sulphuric acid solns of oxygenant at 20 DEG C during 1 to 12min, etching ABS (acrylonitrile-butadiene-styrene copolymer) and PC/ABS (mixture of 45% polycarbonate and 55% acrylonitrile-butadiene-styrene copolymer).After etching, by plastics submergence 1 to 2min in the room temperature neutralization solution comprising 10g/l NaOH, subsequently at the true solution (5min of palladium compound, 20 DEG C) or the middle activation of colloidal solution (2min, 35 DEG C) (colloidal solution is the special solution of DOW Chemical Company (" DOW ")).PdCl in true solution ₂concentration is 0.1g/l, and pH value of solution is 2.7.In true Pd solution after activation, plastics are made to keep 5min at 60 DEG C in pH 9 solution comprising 20g/l sodium hypophosphite.In special adhesive liquid solution after activation, utilize the special acceleration solution of DOW at 40 DEG C of process plastics 2min.Subsequently, plastics nickel plating is made with the Niposit-PM nickel plating process of DOW.Coating quality according to many factors evaluation, the frosting of such as complete or incomplete plating, plating or the plastisol insulating support of non-plating and the adhesion strength of electroless nickel and plastics.In order to evaluate sticking power, in electrochemical copper bath, Ni coating is thickened, and measure from the intensity (kg/cm) needed for the wide bar of plastics stripping 1cm.For ABS test specimen, the etching period in permanganate solution is 5min, is 15min to PC/ABS test specimen.For all test specimens, the etching period in solution of chlorate is 5min.For under the result display of metallized plastics pretreatment condition and metallization (electroless nickel plating) with in following table 2.

Table 2

* in special DOW colloidal solution, (all the other activate in ion activation solution) is activated.

Test specimen 1 to 4 shows, and when based on permanganate etch, the plastisol isolator of support is by electroless nickel part plating, and when etching based on oxymuriate, isolator keeps clean.In addition, when the oxymuriate etching for both ion and colloidal activating solution, the adhesion value between Ni coating and ABS is significantly higher.

Observe identical result when PC/ABS (test specimen 5 to 8) electroless nickel plating: in oxymuriate engraving method, plastisol isolator not plating, and adhesion value is significantly higher, especially when using ion activation solution.

As the KClO in etching solution ₃when concentration is lower than 0.5g/l, ABS is not by plated with electroless nickel, or incomplete plating (test specimen 9).At KClO ₃when concentration is more than 5g/l (test specimen 10), over etching after etching 5min, therefore, coating adhesion value significantly lower (being not enough to for practical application).Exceeding the KClO of suggestion ₃during concentration value, also similar results (test specimen 11 and 12) is obtained to PC/ABS metallization.

H in the etch solution ₂sO ₄when concentration is lower than 50% volume, etching reagent is effective not, and therefore, plastics are not by plated with electroless nickel, or incomplete plating (test specimen 13).At H ₂sO ₄when concentration is higher than 80% volume (test specimen 14), there is plastics over etching, and the sticking power deficiency between chemical nickel coating and plastics.

embodiment 2

ABS plastic (Novodur P2MC, purchased from Ineos) the circular base dish with 7cm diameter is fixed on Stainless Steel Wire.Then, as specified in table 4, matrix being immersed different pretreatments etching solution of the present invention 22 DEG C of temperature and experiences 4 minutes (method order is shown in table 3).Subsequently, underwater cleaning matrix is being flowed about 1 minute.Cleaning subsequently, in and (method steps A i)) and brief immersion 300ml/l 36% hydrochloric acid soln (method steps A ii)) after, based on palladium colloid (Adhemax Aktivator NA, purchased from Atotech, 100ppm palladium) colloidal activating dose at 40 DEG C of activated matrix 3 minutes (method steps B)).

After cleaning subsequently, remove palladium particle protective shells 3 minutes (Adhemax ACC1 accelerator, purchased from Atotech, method steps B i) at 40 DEG C).Make matrix subsequently at 45 DEG C without nickel plating under foreign current 10 minutes (Adhemax LFS, derives from Atotech, method steps B ii)), cleaning, and in room temperature at 3.5A/dm ²copper facing 70 minutes (Cupracid HT, derives from Atotech, method steps C)).After cleaning, plate is stored 60 minutes (method steps C i) at 70 DEG C).Subsequently, cut out with cutter the metallized plastic substrate bar that width is about 1cm, with Tensile Tester (purchased from Instron), metal level is pulled away from plastics (ASTM B 533 1985,2009 pass through again).Obtain adhesion strength as shown in table 4.

Table 3: the order of method steps in embodiment 2

Table 4: according to the adhesion strength of embodiment 2 copper/nickel dam on different ABS mixture

Become apparent from table 4, selecting perchlorate concentration by combining carefulness with sulfuric acid, very high adhesion value can be obtained.Test specimen 1 shows, and the low concentration as 0.2g/l Potcrate (is equivalent to the ClO of 0.0016mol/l ₃ ^-concentration) be enough to obtain excellent sticking power.Maximum value obtains in about 1.5g/l Potcrate scope.Subsequently, observable adhesion strength declines.It should be noted that, compare with only wrapping in vitriolated solution to etch, comprise the composition (table 4, test specimen 9 to 16) of sulfuric acid and phosphate mixture generally in the adhesion value that identical chloranion concentration display is higher, therefore particularly preferably.

Claims

1. make the method for the nonconductive plastic material surface metalation of goods, said method comprising the steps of:

A) described frosting is etched with in the etching aqueous solution;

B) with frosting described in the solution-treated of metallic colloid or metallic compound, described metal is selected from periodic table of elements I group 4 transition metal and periodic table of elements group VIII transition metal; And

C) described metallization of plastic surface is made with metallization solution;

It is characterized in that described etching solution comprises the chloranion source and 50-80% volume sulfuric acid obtaining 0.0016 to 0.12mol/l chloranion concentration.

2. the method for claim 1, is characterized in that at method steps A) in chloranion source in etching solution be selected from sodium chlorate and Potcrate.

3. the method any one of aforementioned claim, is characterized in that chloranion concentration is 0.003mol/l-0.08mol/l.

4. the method for claim 1 and 2, is characterized in that chloranion concentration is 0.01mol/l-0.06mol/l.

5. the method for claim 1 and 2, is characterized in that chloranion concentration is 0.004mol/l-0.04mol/l.

6. the method any one of aforementioned claim, is characterized in that sulfate ion concentration is 60% volume-70% volume.

7. the method any one of aforementioned claim, it is characterized in that described etching solution comprises the second oxygenant of the amount of 2 to 20g/l further, described second oxygenant has the standard oxidation potential exceeding chloranion.

8. the method any one of aforementioned claim, is characterized in that described etching solution comprises phosphoric acid further.

9. the method for claim 8, is characterized in that phosphoric acid concentration is 10% volume-30% volume.

10. the method any one of aforementioned claim, is characterized in that method steps B) in metal be palladium.

Method any one of 11. aforementioned claims, it is characterized in that described frosting is made up of at least one nonconductive plastic material, and described at least one nonconductive plastic material is selected from the mixture of acrylonitrile-butadiene-styrene copolymer, polymeric amide, polycarbonate and acrylonitrile-butadiene-styrene copolymer and other polymkeric substance of at least one.

Method any one of 12. aforementioned claims, is characterized in that at method steps A) and B) between carry out following other method steps:

A i) process described frosting comprising in the solution for the reductive agent of chloranion.

The method of 13. claims 12, is characterized in that described reductive agent is selected from hydroxylammonium sulfate, hydroxylammonium chloride and hydrogen peroxide.

Method any one of 14. aforementioned claims, is characterized in that at method steps A) and B) between carry out following other method steps:

A i) containing comprise hydroxyl ion source neutralizing agent solution in process described frosting.

Method any one of 15. aforementioned claims, is characterized in that at method steps B) and C) between carry out following other method steps:

B i) in acidic aqueous solution, process described frosting, and

B ii) in metallization solution, make described frosting electroless metallising.