CN1329554C - Method for chemical plating metal for non-metal substrate surface and pretreatment system used thereof - Google Patents
Method for chemical plating metal for non-metal substrate surface and pretreatment system used thereof Download PDFInfo
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- CN1329554C CN1329554C CNB2004100228300A CN200410022830A CN1329554C CN 1329554 C CN1329554 C CN 1329554C CN B2004100228300 A CNB2004100228300 A CN B2004100228300A CN 200410022830 A CN200410022830 A CN 200410022830A CN 1329554 C CN1329554 C CN 1329554C
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Abstract
The present invention discloses a surface chemical metal coating method for nonmetal matrixes by means of a new non-noble metal activating new technology and activating solution. The activating solution is alkaline organic metal complex solution which is prepared from the water soluble salt of bivalent nickel ions, copper ions or cobalt ions, organic complexing agent containing amino paraffin hydrocarbon and hydroxy paraffin hydrocarbon and pH regulator. The activating treatment solution and the technology of the present invention can replace the original noble metal activating technology and be widely applied to the field of surface chemical metal coating for nonmetal matrixes, such as chemical nickel plating, chemical copper plating, chemical cobalt plating, etc. The activating solution of the present invention is stable; the technology has simple operation, low cost and capability of effectively saving noble metal resources, and is an ideal technology for replacing the existing noble metal activating technology.
Description
Technical field
The present invention relates to a kind of method of non-metallic substrate surface metalation, particularly a kind of adopt base metal pre-treatment system to the non-metallic substrate surface activate, the method for chemical plating of metal and the activating treatment agent that is adopted thereof again after reduction is handled.
Technical background
Chemical plating of metal is a kind of metal film coating method commonly used.Can on metal and nonmetal basal body, carry out.When implementing nonmetal chemical plating, must implement the technology of a kind of being called " activation ", as the pre-treatment of chemical plating, traditional activating process comprises use SnCl
2Sensitization and PdCl
2Activate two steps,, have cost height, complex process and occur the precious metals pollution plating bath easily, cause drawbacks such as the easy decomposition of chemical plating groove liquid though this technology has characteristics such as activation effect is good, technology is simple.Though having proposed various use silane coupling agents, someone make noble metal supports such as Pd at treated lip-deep method (Japanese patent gazette No.S59-52701, the open No.S60-1 81294 of Japanese patent application book, the open No.S61-194183 of Japanese patent application book, Japanese patent gazette No.H03-44149, CN1406288A), but these methods are at polyurethane sponge, non-woven fabrics, cotton, chemical ﹠ blended fabric, fibrous reticulum, be difficult to form to adhere to the good homogeneous rete on the non-metallic material such as cloth, follow-up electroless plating effect is affected and is difficult to promote the use of.
In recent years, the someone has proposed to use non-noble metal process for activating, and Gao Deshu etc. (research [J] of non-metal electroplating colloid activation solution, sufacing, 1993,22) use NaBH with the hydroxide colloid solution impregnation ABS plastic matrix of nickel, copper
4Reduction nickelous, copper are metallic state, and electroless plating obtains certain effect then, but the bonding force of coating is poor, the active activator of making far below palladium salt, and be difficult to reach covering fully.Also has report (chemical plating of non-metal material nickel activating process research; material protection; the 34th the 2nd phase of volume of February calendar year 2001) with high density ammino nickel salt pottery or soda glass are activated; then under the temperature more than 200 ℃ with absorption the nickel salt pyrolysis be material with high catalytic activity; implement electroless plating again; also can receive better chemical plating effect; but its too high pyrolysis temperature can not be used for the lower base materials of thermal degradation temperature such as polyurethane sponge, non-woven fabrics, cotton, chemical ﹠ blended fabric, fibrous reticulum, cloth, and range of application is restricted.
Summary of the invention
The present invention aims to provide a kind ofly can save the precious metal resource, cost is low, pollution is little, be suitable for large-scale industrial production, the pre-treating technology and the pre-treatment system that are complementary with existing chemical plating of metal technology.
The present invention adopts following proposal:
A kind of pre-treatment system that is used for the non-metallic substrate surface metalation is characterized in that: described system is made up of activated solution and two independent sectors of reducing solution; The metallo-organic complex basic solution be made up of the organic complexing agent and the pH regulator agent of the bivalent ions water-soluble salt of transition metal, amino-contained and hydroxyl of activated solution wherein, transition metal are selected from a kind of in nickel, copper, the cobalt; Reducing solution is made up of reductive agent and pH regulator agent.
Described complexing agent is amino-contained and hydroxyl and organism that contain 2～10 carbon atoms, as trolamine, N methyldiethanol amine, and 1-dimethylin-2-propyl alcohol, DBAE dibutylamino ethanol etc.In the metallo-organic complex basic solution, the total concn of transition metal is 0.003～0.20mol/L, the concentration of complexing agent is 0.006～0.5mol/L, pH value is 8～14, alkali metal hydroxide commonly used is adopted in the pH regulator agent, as: NaOH, KOH etc., also can adopt the conditioning agent that mixes that ammoniacal liquor and alkali metal hydroxide commonly used and solubility ammonium salt commonly used form, as: NaOH-(NH
4)
2S0
4, KOH-NH
4C1 etc.
Reductive agent is one or both in the following compound in the described reducing solution: POTASSIUM BOROHYDRIDE, sodium borohydride, hydrazine hydrate, hypophosphite and amido boranes; The pH regulator agent can be adopted ammoniacal liquor, also can adopt the conditioning agent that mixes of alkali metal hydroxide commonly used and solubility ammonium salt commonly used composition, as: NaOH-(NH
4)
2SO
4, KOH-NH
4C1 etc.
Metallized Technology is carried out on a kind of non-metallic substrate surface.Non-metallic substrate makes it conductionization after passing through surface preparation, activation, reduction, chemical plating of metal operation continuously.It is characterized in that: the activation treatment operation adopts the metallo-organic complex basic solution of being made up of the organic complexing agent and the pH regulator agent of the bivalent ions water-soluble salt of transition metal, amino-contained and hydroxyl, and transition metal is selected a kind of in nickel, copper, the cobalt for use.
Non-metallic substrate adopts a kind of in the following base material: polyurethane sponge, non-woven fabrics, cotton, chemical ﹠ blended fabric, fibrous reticulum, cloth, plastic cement, glass, pottery.
Described complexing agent is amino-contained and hydroxyl and organic compound that contain 2～10 carbon atoms, as trolamine, N methyldiethanol amine, and 1-dimethylin-2-propyl alcohol, DBAE dibutylamino ethanol etc.
The pH value of described metallo-organic complex basic solution is 8～14, alkali metal hydroxide commonly used is adopted in the pH regulator agent, as: NaOH, KOH etc., can adopt the conditioning agent that mixes that ammoniacal liquor and alkali metal hydroxide commonly used and solubility ammonium salt commonly used form, as: NaOH-(NH
4)
2SO
4, KOH-NH
4Cl etc.
In the described metallo-organic complex basic solution, the total concn of transition metal is 0.003～0.20mol/L, and the concentration of complexing agent is 0.006～0.5mol/L.
The temperature of activation procedure is 20～70 ℃.
In the aqueous solution of the following compound of reductive agent employing in the described reduction operation one or both: POTASSIUM BOROHYDRIDE, sodium borohydride, hydrazine hydrate, hypophosphite and amido boranes, reductant concentration is 0.5～20g/L, and the temperature of reduction operation is 20～80 ℃.
In the chemical plating of metal operation, can be a kind of in nickel, copper or the cobalt at the metal of substrate surface plating.
Concrete technology is as follows:
(1) surface preparation non-metallic substrate to be plated at first need pass through surface preparation, and this process comprises oil removing, alligatoring, striping.Degreasing fluid is generally alkaline wash or organic cleaning fluid; Coarsening solution is the mixed solution that chromic anhydride or potassium bichromate and the vitriol oil are made into, or the mixed solution that is made into of potassium permanganate and the vitriol oil; Striping liquid is the solution that weak reductant is mixed with, as oxalic acid solution etc.
(2) the activation non-metallic substrate enters in the activation solution in 20～70 ℃ of activation 0.5～8min after surface preparation and cleaning.The metallo-organic complex basic solution that activated solution is made up of the organic complexing agent and the pH regulator agent of the bivalent ions water-soluble salt of transition metal, amino-contained and hydroxyl.Transition metal is selected a kind of in nickel, copper, the cobalt for use; Complexing agent be contain amino and hydroxyl and 2～10 carbon atom organism are arranged, as trolamine, N methyldiethanol amine, 1-dimethylin-2-propyl alcohol, DBAE dibutylamino ethanol etc.; Alkali metal hydroxide commonly used is adopted in the pH regulator agent, as: NaOH, KOH etc.The total concn of transition metal is 0.003～0.20mol/L in the solution, and the concentration of complexing agent is 0.006～0.5mol/L, and the pH value of system is 8～14.
(3) reduction reduction process of the present invention is meant the process that the activation postadhesion is reduced to the zero-valent state transition metal with catalytic activity in the lip-deep complexing transition metal ion of non-metallic substrate.Reduced liquid is made up of reductive agent and pH regulator agent, reductive agent adopts one or both in the following compound: POTASSIUM BOROHYDRIDE, sodium borohydride, hydrazine hydrate, hypophosphite and amino borane class reductive agent, the concentration of reductive agent is 0.5～20g/L, the pH regulator agent can be adopted ammoniacal liquor, also can adopt the conditioning agent that mixes of alkali metal hydroxide commonly used and solubility ammonium salt commonly used composition, as: NaOH-(NH
4)
2SO
4, KOH-NH
4Cl etc. make the pH value of reducing solution maintain 10～11.Non-metallic substrate after activated enters in the above-mentioned reducing solution, and keeping the reduced liquid temperature is 30～80 ℃, and the recovery time is 0.5～8min.
(4) the enforceable electroless plating system of electroless plating the present invention mainly contains electroless plating systems such as chemical nickel plating, electroless cobalt plating, electroless copper, adopts conventional chemical depositing process and chemical plating solution.
Compared with prior art, the present invention has the following advantages:
1. adopt electroless plating pre-treatment system of the present invention and technology,, therefore can save the precious metal resource, can reduce production costs significantly in the industrial production, overcome the bottleneck that reduces cost in the chemical plating technology owing to do not need to use precious metal such as palladium.
2. adopt pre-treatment system of the present invention non-metallic substrate to be carried out in the technology of surperficial pre-treatment, the reduction operation adopts the water solution system of reductive agent, reduction temperature is controlled at 30～80 ℃, with the employing of prior art bibliographical information more than 200 ℃ the high temperature reduction technology compare, greatly reduce reduction temperature, can be applicable to the organic substrate of degradation temperature restriction.Expanded the scope of industrial application significantly.
3. in pre-treatment system of the present invention and the technology, provide the transition metal ion in catalytic metal source stable under normal condition, the alkaline complex compound solution activation system that forms is stable, therefore the controllability of this technology is good, be very suitable for large-scale industrial production, be particularly useful in the fields such as continuous chemical nickel plating, electroless cobalt plating, electroless copper of band, silk material, using.
4. scale production practice shows, adopt the technology of pre-treatment of the present invention after, chemical plating of metal can form homogeneous coating stable, that bonding force is good, with the SnCl of widespread use in the present production again
2Sensitization-PdCl
2The effect unanimity of activation pretreatment technology.
5. pre-treatment system of the present invention and technology and existing electroless plating surface pretreatment process matched are good, and existing installation almost need not to do any change, and only need tank liquor is changed and can be come into operation, and the scrap build investment is very little.
Embodiment
Embodiment 1
Polyurethane sponge soaks 3min in 30 ℃ degreasing fluid; After taking-up was cleaned, alligatoring 4min in 30 ℃ of coarsening solutions put into striping liquid after taking-up is cleaned and soaks 3min; Take out and clean, put into 50 ℃ of activation solutions and activate 1～2min; Reduce under 50 ℃ in reduced liquid 1～2min the clean back of taking-up.The rinsing of reductive polyurethane sponge is clean, put into 50 ℃ of following reaction 2～5min of chemical nickel plating system and promptly finish nickel process.Each solution composition is as follows:
A degreasing fluid sodium hydroxide 0.7～0.9 mol/L
B coarsening solution potassium permanganate 0.6～0.8 g/L
Sulfuric acid 0.12～0.15 g/L
pH 2.3～2.8
C striping liquid oxalic acid 10～14 g/L
D activation solution trolamine 0.08～0.10 mol/L
Single nickel salt (NiSO
46H
2O) 0.017～0.021 mol/L
Sodium hydroxide is an amount of
pH 13～13.5
E reduced liquid POTASSIUM BOROHYDRIDE 0.6～1.0 g/L
Ammonium sulfate-sodium hydroxide is an amount of
pH 10.3～10.8
F chemical nickel-plating solution single nickel salt (NiSO
46H
2O) 21.5～24.5 g/L
Inferior sodium phosphate (NaH
2PO
2H
2O) 22.5～25.5 g/L
Trisodium Citrate (Na
3C
6H
5O
72H
2O) 55～65 g/L
Ammoniacal liquor is an amount of
pH 8.4～8.8
Embodiment 2
Woven dacron soaks 25min in 95 ℃ degreasing fluid; After taking-up is cleaned, put into activation solution and activate 4～6min down for 25 ℃; Reduce under 25 ℃ in reduced liquid 4～6min the clean back of taking-up.The rinsing of reductive woven dacron is clean, put into 20 ℃ of following reaction 2～5min of electroless copper system and promptly finish the electroless copper process.Each solution composition is as follows:
A degreasing fluid sodium hydroxide 100 g/L
B activation solution trolamine 0.008～0.015 mol/L
Copper sulfate (CuSO
45H
2O) 0.004～0.006 mol/L
Ammoniacal liquor is an amount of
pH 11～12
C reduced liquid POTASSIUM BOROHYDRIDE 5～6 g/L
Ammonium sulfate-sodium hydroxide is an amount of
pH 10.3～10.8
D chemical bronze plating liquid copper sulfate (CuSO
45H
2O) 5～10 g/L
Seignette salt (NaKC
4H
4O
54H
2O) 20～25 g/L
Sodium hydroxide 10～15 g/L
Formaldehyde (37%) 8～12 ml/L
pH 12.5～13
Embodiment 3
ABS plastic is soaked 10min in 60 ℃ degreasing fluid; After taking-up was cleaned, alligatoring 20min in 60～70 ℃ of coarsening solutions put into striping liquid after taking-up is cleaned and soaks 3min; After taking-up is cleaned, put into activation solution and activate 6～8min down for 65 ℃; Reduce under 75 ℃ in reduced liquid 6～8min the clean back of taking-up.The rinsing of reductive woven dacron is clean, put into 40 ℃ of following reaction 2～5min of electroless cobalt plating system and promptly finish the electroless cobalt plating process.Each solution composition is as follows:
A degreasing fluid sodium hydroxide 40 g/L
B coarsening solution chromic anhydride 400～430 g/L
Sulfuric acid 330～405 g/L
C striping liquid hydrochloric acid 100～200 ml/L
D activation solution N methyldiethanol amine 0.40～0.50 mol/L
Cobalt chloride (CoCl
27H
2O) 0.16～0.18 mol/L
Sodium hydroxide-ammonium sulfate is an amount of
pH 8.3～9.0
E reduced liquid sodium borohydride 0.2～0.5 g/L
Inferior sodium phosphate (NaH
2PO
2H
2O) 16～20 g/L
Ammonium chloride-sodium hydroxide is an amount of
pH 10.3～10.8
F electroless cobalt plating solution chlorination cobalt (CoCl
26H
2O) 18.5～21.5 g/L
Sodium borohydride (NaBH
4) 8.0～9.5 g/L
Seignette salt 55～60 g/L
Ammoniacal liquor is an amount of
pH 12.3～13.0
Embodiment 4
Biscuit ware soaks 10min in 60 ℃ degreasing fluid; After taking-up was cleaned, alligatoring 4～6min in 20～30 ℃ of coarsening solutions put into striping liquid after taking-up is cleaned and soaks 3min; After taking-up is cleaned, put into activation solution and activate 6～8min down for 70 ℃; Reduce under 50 ℃ in reduced liquid 5～7min the clean back of taking-up.The rinsing of reductive biscuit ware is clean, put into 50 ℃ of following reaction 2～5min of chemical nickel plating system and promptly finish nickel process.Each solution composition is as follows:
A degreasing fluid sodium hydroxide 40 g/L
B coarsening solution chromic anhydride 50 g/L
Sulfuric acid 180 ml/L
Hydrofluoric acid 100 ml/L
C striping liquid hydrochloric acid 100～200 ml/L
D activation solution 1-dimethylin-2-propyl alcohol 0.12～0.20 mol/L
Single nickel salt (NiSO
46H
2O) 0.038～0.049 mol/L
Sodium hydroxide is an amount of
pH 12.3～13.0
E reduced liquid hydrazine hydrate 5～6 g/L
Ammonium chloride-sodium hydroxide is an amount of
pH 10.3～10.8
F chemical nickel-plating solution single nickel salt (NiSO
46H
2O) 21.5～24.5 g/L
Inferior sodium phosphate (NaH
2PO
2H
2O) 22.5～25.5 g/L
Trisodium Citrate (Na
3C
6H
5O
72H
2O) 55～65 g/L
Ammoniacal liquor is an amount of
pH 8.4～8.8
Embodiment 5
Glass soaks 5min in 60 ℃ degreasing fluid; After taking-up was cleaned, alligatoring 20min in 60～70 ℃ of coarsening solutions put into striping liquid after taking-up is cleaned and soaks 3min; After taking-up is cleaned, put into 70 ℃ of activation of activation solution, 4～6min; Reduce under 60 ℃ in reduced liquid 4～6min the clean back of taking-up.Glass rinsing after the reduction is clean, put into 50 ℃ of following reaction 2～5min of chemical nickel plating system and promptly finish nickel process.
Each solution composition is as follows:
A degreasing fluid sodium hydroxide 40 g/L
B coarsening solution potassium bichromate 100 g/L
Sulfuric acid 180 ml/L
Hydrofluoric acid 100 ml/L
C striping liquid hydrochloric acid 100～200 ml/L
D activation solution DBAE dibutylamino ethanol 0.12～0.20 mol/L
Single nickel salt (NiSO
46H
2O) 0.038～0.049 mol/L
Sodium hydroxide is an amount of
pH 12.5～13.5
E reduced liquid POTASSIUM BOROHYDRIDE 2.5～4.0 g/L
Ammonium chloride-potassium hydroxide is an amount of
pH 10.3～10.8
F chemical nickel-plating solution single nickel salt (NiSO
46H
2O) 21.5～24.5 g/L
Inferior sodium phosphate (NaH
2PO
2H
2O) 22.5～25. g/L
Trisodium Citrate (Na
3C
6H
5O
72H
2O) 55～65 g/L
Ammoniacal liquor is an amount of
pH 8.4～8.8
Claims (7)
1, a kind of method of non-metallic substrate surface metalation, after non-metallic substrate passes through surface preparation, activation, reduction, chemical plating of metal operation continuously, make it conductionization, it is characterized in that: the activation treatment operation adopts the metallo-organic complex basic solution of being made up of the bivalent ions water-soluble salt of transition metal, amino-contained and hydroxyl and organic complexing agent that contain 2～10 carbon atoms and pH regulator agent, and transition metal is selected from a kind of in nickel, copper, the cobalt; In the metallo-organic complex basic solution system, the total concn of transition metal is 0.003～0.20mol/L, and the concentration of complexing agent is 0.006～0.5mol/L.
2, the method for non-metallic substrate surface metalation according to claim 1 is characterized in that: non-metallic substrate adopts a kind of in the following base material: polyurethane sponge, non-woven fabrics, cotton, chemical ﹠ blended fabric, fibrous reticulum, cloth, plastic cement, glass, pottery.
3, the method for non-metallic substrate surface metalation according to claim 1 is characterized in that: the pH value of metallo-organic complex basic solution is 8～14.
4, non-metallic substrate method for surface metallation according to claim 1 is characterized in that reductive agent in the described reduction operation adopts one or both in the aqueous solution of following compound: POTASSIUM BOROHYDRIDE, sodium borohydride, hydrazine hydrate, hypophosphite and amido boranes.
5, non-metallic substrate method for surface metallation according to claim 1 is characterized in that in the electroless plating, can be a kind of in nickel, copper or the cobalt at the metal of substrate surface plating.
6, a kind of pre-treatment system that is used for the non-metallic substrate surface metalation is characterized in that: described system is made up of activated solution and two independent sectors of reducing solution; Wherein activated solution by the bivalent ions water-soluble salt of transition metal, amino-contained and hydroxyl and contain the metallo-organic complex basic solution that 2～10 carbon atom organic complexing agents and pH regulator agent are formed, transition metal is selected from a kind of in nickel, copper, the cobalt; Reducing solution is made up of reductive agent and pH regulator agent, one or both in the aqueous solution of the following compound of reductive agent employing: POTASSIUM BOROHYDRIDE, sodium borohydride, hydrazine hydrate, hypophosphite and amido boranes.
7, the pre-treatment system of non-metallic substrate surface metalation according to claim 6 is characterized in that: in the activated solution, the total concn of transition metal is 0.003～0.20mol/L, and the concentration of complexing agent is 0.006～0.5mol/L.
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| CNB2004100228300A CN1329554C (en) | 2004-01-13 | 2004-01-13 | Method for chemical plating metal for non-metal substrate surface and pretreatment system used thereof |
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|---|---|---|---|
| CNB2004100228300A CN1329554C (en) | 2004-01-13 | 2004-01-13 | Method for chemical plating metal for non-metal substrate surface and pretreatment system used thereof |
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| CN1329554C true CN1329554C (en) | 2007-08-01 |
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| CN1641070A (en) | 2005-07-20 |
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