Title of Invention	IMPROVED METHOD FOR THE DIRECT METALLIZATION OF ELECTRICALLY NON-CONDUCTIVE SUBSTRATE SURFACES, IN PARTICULAR POLYIMIDE SURFACES
Abstract	The present invention relates to an improved method for the direct metallization of non-conductive substrate surfaces, in particular polyimide surfaces, that is characterized by the process steps of etching the substrate surface with an acidic etching solution that contains peroxide; contacting the etched substrate surface with an acidic treatment solution that contains permanganate; activating the treated substrate surface in an acidic activation solution that contains peroxide; contacting the activated substrate surface with an acidic catalytic solution that contains at least a thiophen derivate and at least a sulphonic acid derivate; metallization of the thus treated substrate surface in an acidic galvanic metallization bath.

Title of Invention

IMPROVED METHOD FOR THE DIRECT METALLIZATION OF ELECTRICALLY NON-CONDUCTIVE SUBSTRATE SURFACES, IN PARTICULAR POLYIMIDE SURFACES

Abstract

The present invention relates to an improved method for the direct metallization of non-conductive substrate surfaces, in particular polyimide surfaces, that is characterized by the process steps of etching the substrate surface with an acidic etching solution that contains peroxide; contacting the etched substrate surface with an acidic treatment solution that contains permanganate; activating the treated substrate surface in an acidic activation solution that contains peroxide; contacting the activated substrate surface with an acidic catalytic solution that contains at least a thiophen derivate and at least a sulphonic acid derivate; metallization of the thus treated substrate surface in an acidic galvanic metallization bath.

Full Text	Improved method for the direct metallization of electrically non-conductive substrate surfaces, in particular polvimide surfaces The present invention relates to an improved method for the direct metallization of electrically non-conductive substrate surfaces, in particular polyimide surfaces. The direct metallization of electrically non-conductive substrates plays an important role in particular in the manufacture of printed circuits boards within the context of modern manufacturing processes. Usually, printed circuits boards are made of glass fibre reinforced epoxy resins, polyimides or other suitable polymeric plastics. Such printed boards are often manufactured as multilayer circuits, in which different conduction pattern layers are superimposed. The single connection layers have to be connected to each other by so-called throughplatings. Both for the application of the conduction patterns by means of masks or other suitable methods and for the generation of a sufficient conductivity within the throughplatings, not only chemical copper deposition methods but also direct metallization methods are used in the state of the art. Besides these applications, the direct metallization of plastics is also used in the field of decorative coatings, such as for example in the field of fittings technique, manufacture of jewellery or the automotive industry. In the state of the art it has been common since some time to directly coat galvanically non-conductive plastic substrates while renouncing to a previous chemical metallization. Such a method is for example described in US-PS 30 99 608 and DE-OS 33 04 004. However, the methods described there have not been used in practice. This was over all due to the fact that only freshly prepared solutions could obtain relatively usable results. Shortly after initiation of these ones, the quality of the obtained metal deposition decreased, such that only insufficient results were still achieved. From the German published specifications DE 1 299 740, DE 2 926 335 A1 and DE 31 32 218 A1 methods for the manufacture of throughplatings of printed circuits using conductive lacquers as well as a subsequent galvanic or currentless metallization are furthermore known. From the German patent DE 38 06 884 C1 a method for the manufacture of throughplated printed boards on the base of a polymeric carrier material or ceramic by galvanic or currentless application of a metal layer onto the surfaces, which are not coated with a conducting metal layer, is known that is characterized in that the carrier is pre-treated in an oxidizing bath, after removal of the bath residues by rinsing the carrier is introduced into a bath which contains a monomer, in particular pyrrole or pyrrole derivates, that is electrically conducting in polymeric form, and afterwards the thus treated substrate is introduced into an acid bath, wherein an electrically conducting layer of polymerized pyrrole or pyrrole derivates is formed, whereupon bath residues are removed by rinsing, if necessary, and a galvanic metallization is carried out. Based upon this state of the art, it is the o b j e c t of the present invention to provide an improved method for the direct metallization of non-conductive substrate surfaces, in particular polyimide surfaces. This aim is achieved by a method for the direct metallization of non-conductive substrate surfaces, in particular polyimide surfaces, that is characterized by the process steps: - etching the substrate surface with an acidic etching solution that contains peroxide or peroxosulfate - contacting the etched substrate surface with an acidic treatment solution that contains permanganate - activating the treated substrate surface in an acidic activation solution that contains an oxidizing agent - contacting the activated substrate surface with an acidic treatment solution that contains at least a thiophen derivate and at least a sulphonic acid or a sulphonic acid derivate and - metallization of the thus treated substrate surface in an acidic galvanic metallization bath. Such method for the direct metallization of non-conducting substrate surfaces improves the state of the art in that a reliable direct metallization of non-conductive substrate surfaces under clearly more economic and more ecologic process conditions becomes possible. Such a process sequence in particular permits to use clearly smaller quantities of chemicals in the individual treatment solutions, which leads to a reduced environmental load. Furthermore, in comparison to the state of the art, the process sequence according to the invention permits to work with clearly reduced treatment temperatures. Hereby, additional economic and ecologic advantages can be obtained. In an embodiment of the method according to the invention, the etchant comprises between about 30 g/l and about 120 g/l peroxide and an acid selected from the group consisting of sulphuric acid, methane sulphonic acid, methane disulphonic acid or phosphoric acid. Advantageously, the temperature can be room temperature during the etching step, whereby supplementary heating devices and energy costs related thereto can be omitted. Suitable peroxides are for example salts of the peroxide sulphuric acid and/or the peroxisulphuric acid. In an advantageous embodiment of the method according to the invention the etched substrate surfaces are contacted with a treatment solution containing permanganate, which comprises between about 30 g/l and 60 g/l permanganate in the form of potassium or sodium permanganate and an acid selected from the group consisting of sulphuric acid, phosphoric acid, methane sulphonic acid and methane disulphonic acid. According to the invention, the pH value of the permanganate containing treatment solution is According to the invention, the temperature during contacting the etched substrate surfaces with the permanganate containing treatment solution can be comprised between 40 and 70°C, preferably between 50 and 60°C. Subsequently, the substrate surfaces that have been contacted with the acid permanganate containing treatment solution are activated in an acid peroxosulphate containing activation solution, which comprises between about 30 g/l and about 120 g/l peroxosulphate and an acid selected from the group consisting of sulphuric acid, methane sulphonic acid, methane disulphonic acid and phosphoric acid. Advantageously, the activator solution, with respect to the composition thereof, corresponds to the etching solution. In an embodiment of the method according to the invention, the activation in the above described activation solution is carried out with ultrasonic agitation. For this, an ultrasonic generator can be introduced into an activation bath or be placed on this one. Following the activation of the substrate surfaces to be metallized, these ones are contacted with a catalytic solution that comprises at least a thiophen derivate and at least a sulphonic acid or a sulphonic acid derivate, and that preferably comprises 3,4-ethylendioxythiophen as thiophen derivate and polystyrene sulphonic acid as sulphonic acid derivate. The thus treated substrate surfaces can subsequently be metallized in an appropriate electrolyte for the galvanic deposition of metal layers. Such an electrolyte can be for example an acid copper comprising electrolyte for the deposition of copper layers. In another embodiment of the method according to the invention, the treated substrate surface can be rinsed in an acid rinsing solution, preferably in a sulphuric acid rinsing solution, before a galvanic coating with a metallic layer. It is within the scope of the invention that rinsing steps are carried out between the individual treatment steps. It is a special advantage of the method according to the invention that, with the exception of the step of contacting the substrate surface with an acid permanganate containing treatment solution, all process steps can be carried out at room temperature. This is in particular a reason why significant advantages can be achieved in comparison to the methods known from the state of the art, since additional devices for setting the temperature of the process solutions can be omitted. The treatment times of the individual process steps, with the exception of the galvanic metallization, are in a range comprised between about 1 and 3 minutes. The activation of the substrate surface that has been contacted with the acidic permanganate containing treatment solution in the acidic peroxosulphate containing activation solution can even be carried out in less than 1 minute. The same is true for the step of optionally contacting the treated substrate surface with an acidic, preferably sulphuric acid containing rinsing solution before a galvanic metallization. The following exemplary embodiment is exemplarily representative of the method according to the invention which shall not be limited to the exemplary embodiment. Example No. 1 A polyamide substrate having the size of 600 x 500 mm was submitted to the following treatment steps. 3 min. etching for example 100 g/l sodium peroxidisulphate 50 g/l sulphuric acid room temperature rinsing 3 min. conditioning commercial conditioner for example 40 ml/I conditioner room temperature up to 40°C rinsing 3 min. activating in permanganate containing acid solution for example 50 g/l potassium permanganate methane sulphonic acid for setting the pH value to 2.0 +/- 0.1, 50°C rinsing activating the surfaces treated with permanganate for example 100 g/l sodium peroxidisulphate 50 g/l sulphuric acid supported by ultrasonic agitation room temperature rinsing 2-3 min. contacting the activated surfaces with a solution that contains a thiophen derivate for example 10 ml/I of a 3,4-ethylendioxithiophen comprising solution 10 ml/I of a styrene sulphonic acid containing solution about 2 ml/l of a phosphoric acid containing solution for setting the pH value to 2.0 +/- 0.1 room temperature rinsing etching (optional) metallization, for example Envision Cuprostar LP1 Example No. 2 A polyamide substrate having the size of 600 x 500 mm was submitted to the following treatment steps. 3 min. etching for example 80 g/l sodium peroxidisulphate 50 g/l sulphuric acid room temperature rinsing 3 min. conditioning commercial conditioner, for example 40 ml/I conditioner room temperature up to 40°C rinsing 3 min. activating in permanganate containing acid solution for example 40 g/l potassium permanganate methane sulphonic acid for setting the pH value to 2.0 +/- 0.1 50°C rinsing activating the surfaces treated with permanganate for example 80 g/l sodium persulphate (caroate) 50 g/l sulphuric acid supported by ultrasonic agitation room temperature rinsing 2-3 min. contacting the activated surfaces with a solution that contains a thiophen derivate for example 7 ml/I of a 3,4-ethylendioxithiophen comprising solution 7 ml/I of a styrene sulphonic acid containing solution about 2 ml/l of a phosphoric acid containing solution for setting the pH value to 2.0 +/- 0.1 room temperature rinsing etching (optional) metallization, for example Envision Cuprostar LP1 Example No. 3 A polyamide substrate having the size of 600 x 500 mm was submitted to the following treatment steps. 3 min. etching for example 80 ml/1 hydrogen peroxide (33%) 50 g/l sulphuric acid 10 ml/l of a phenolsulphonic acid containing solution room temperature rinsing 3 min. conditioning commercial conditioner, for example 40 ml/l conditioner room temperature up to 40°C rinsing 3 min. activating in permanganate containing acid solution for example 36 g/l sodium permanganate methane sulphonic acid for setting the pH value to 2.0 +/- 0.1 50°C rinsing activating the surfaces treated with permanganate for example 100 g/l sodium peroxidisulphate 50 g/l sulphuric acid supported by ultrasonic agitation room temperature rinsing 2-3 min. contacting the activated surfaces with a solution tnat contains a thiophen derivate for example 10 ml/l of a 3,4-ethylendioxithiophen comprising solution 10 ml/l of a styrene sulphonic acid containing solution about 2 ml/I of a phosphoric acid containing solution for setting the pH value to 2.0 +/- 0.1 room temperature rinsing etching (optional) metallization, for example Envision Cuprostar LP1 Example No. 4 A polyamide substrate having the size of 600 x 500 mm was submitted to the following treatment steps. 3 min. etching for example 100 g/l sodium peroxidisulphate 50 g/l sulphuric acid room temperature rinsing 3 min. conditioning commercial conditioner, in use in house for example 40 ml/I conditioner room temperature up to 40°C rinsing 3 min. activating in permanganate containing acid solution for example 50 g/l potassium permanganate methane sulphonic acid for setting the pH value to 2.0 +/- 0.1, 50°C 1 rinsirfg activating the surfaces treated with permanganate for example 30 g/l sodium peroxidisulphate 50 g/l sulphuric acid supported by ultrasonic agitation room temperature rinsing 2-3 min. contacting the activated surfaces with a solution that contains a thiophen derivate for example 10 ml/l of a 3,4-ethylendioxithiophen comprising solution 10 ml/I of a styrene sulphonic acid containing solution about 2 ml/l of a phosphoric acid containing solution for setting the pH value to 2.0 +/- 0.1 room temperature rinsing etching (optional) metallization, for example Envision Cuprostar LP1 Example No. 5 A polyamide substrate having the size of 600 x 500 mm was submitted to the following treatment steps. 3 min. etching for example 80 g/l sodium peroxidisulphate 50 g/l sulphuric acid room temperature rinsing 3 min. conditioning commercial conditioner, in use in house for example 40 ml/l conditioner room temperature up to 40°C rinsing 3 min. activating in permanganate containing acid solution for example 40 g/l potassium permanganate methane sulphonic acid for setting the pH value to 2.0 +/- 0.1 50°C rinsing activating the surfaces treated with permanganate for example 40 g/l sodium persulphate (caroate) 50 g/l sulphuric acid supported by ultrasonic agitation room temperature rinsing 2-3 min. contacting the activated surfaces with a solution that contains a thiophen derivate for example 7 ml/l of a 3,4-ethylendioxithiophen comprising solution 7 ml/l of a styrene sulphonic acid containing solution about 2 ml/I of a phosphoric acid containing solution for setting the pH value to 2.0 +/- 0.1 room temperature rinsing etching (optional) metallization, for example Envision Cuprostar LP1 Example No. 6 A polyamide substrate having the size of 600 x 500 mm was submitted to the following treatment steps. 3 min. etching for example 80 ml/l hydrogen peroxide (33%) 50 g/l sulphuric acid 10 ml/l of a phenolsulphonic acid solution room temperature rinsing 3 min. conditioning commercial conditioner, in use in house for example 40 ml/l conditioner room temperature up to 40°C rinsing 3 min. activating in permanganate containing acid solution for example 36 g/l sodium permanganate methane sulphonic acid for setting the pH value to 2.0 +/- 0.1 50°C rinsing activating the surfaces treated with permanganate for example 40 g/l sodium peroxidisulphate 50 g/l sulphuric acid supported by ultrasonic agitation room temperature rinsing 2-3 min. contacting the activated surfaces with a solution that contains a thiophen derivate for example 10 ml/l of a 3,4-ethylendioxithiophen comprising solution 10 ml/I of a styrene sulphonic acid containing solution about 2 ml/l of a phosphoric acid containing solution for setting the pH value to 2.0 +/- 0.1 room temperature rinsing etching (optional) metallization, for example Envision Cuprostar LP1 Alternatively, all methods according to the invention indicated in the examples 1 through 6 were carried out with Teflon substrates that had been pre-treated with FR 4 and plasma. We Claim: 1. A method for the direct metallization of non-conductive substrate surfaces, in particular polyimide surfaces, characterized by the method steps: - etching the substrate surface with an acidic etching solution that contains 30 g/l to 120 g/l peroxide - contacting the etched substrate surface with an acidic treatment solution that contains between 40 g/l and 60 g/l permanganate - activating the treated substrate surface in an acidic activation solution that contains between 30 g/l and 120 g/l peroxide - contacting the activated substrate surface with an acidic catalytic solution that contains at least a thiophen derivate and at least a sulphonic acid derivate and - metallization of the thus treated substrate surface in an acidic galvanic metallization bath. 2. A method as claimed in claim 1, wherein rinsing steps are carried out between the individual process steps. 3. A method as claimed in one of the preceding claims, wherein the etchant comprises 80 g/l to 120 g/l peroxide. 4. A method as claimed in one of the preceding claims, wherein the etchant comprises an acid selected from the group consisting of sulphuric acid and phosphoric acid. 5. A method as claimed in one or several of the preceding claims, wherein the permanganate containing treatment solution comprises an acid selected from the group consisting of hydrochloric acid, sulphuric acid, phosphoric acid, methane sulphonic acid and methane disulphonic acid. 6. A method as claimed in claim 5, wherein the treatment solution has a pH value of 7. A method as claimed in one of the preceding claims, wherein the activation solution comprises between 80 g/l and 120 g/l peroxide. 8. A method as claimed in claim 1, wherein the activation solution comprises an acid selected from the group consisting of sulphuric acid, hyrdochloric acid and phosphoric acid. 9. A method as claimed in claim 7 or 8, wherein the activation solution is identical with the etching solution with respect to the composition thereof. 10. A method as claimed in one of the preceding claims, wherein the activation is carried out with ultrasonic agitation. 11. A method as claimed in one or several of the preceding claims, wherein the thiophen derivate and sulphonic acid derivate containing treatment solution comprises at least 3,4-ethylendioxythiophen as thiophen derivate and styrene sulphonic acid as sulphonic acid derivate. 12. A method as claimed in one of the preceding claims, wherein after the treatment with the thiophen derivate and sulphonic acid derivate containing treatment solution the substrate surface is contacted with an acid, preferably sulphuric acid rinsing solution. 13. A method as claimed in one of the preceding claims, wherein the substrate surface is metallized in a copper containing metallization bath.

Full Text

Improved method for the direct metallization of electrically non-conductive substrate
surfaces, in particular polvimide surfaces
The present invention relates to an improved method for the direct metallization of electrically non-conductive substrate surfaces, in particular polyimide surfaces.
The direct metallization of electrically non-conductive substrates plays an important role in particular in the manufacture of printed circuits boards within the context of modern manufacturing processes. Usually, printed circuits boards are made of glass fibre reinforced epoxy resins, polyimides or other suitable polymeric plastics. Such printed boards are often manufactured as multilayer circuits, in which different conduction pattern layers are superimposed. The single connection layers have to be connected to each other by so-called throughplatings. Both for the application of the conduction patterns by means of masks or other suitable methods and for the generation of a sufficient conductivity within the throughplatings, not only chemical copper deposition methods but also direct metallization methods are used in the state of the art.
Besides these applications, the direct metallization of plastics is also used in the field of decorative coatings, such as for example in the field of fittings technique, manufacture of jewellery or the automotive industry.
In the state of the art it has been common since some time to directly coat galvanically non-conductive plastic substrates while renouncing to a previous chemical metallization. Such a method is for example described in US-PS 30 99 608 and DE-OS 33 04 004. However, the methods described there have not been used in practice. This was over all due to the fact that only freshly prepared solutions could obtain relatively usable results. Shortly after initiation of these ones, the quality of the obtained metal deposition decreased, such that only insufficient results were still achieved.
From the German published specifications DE 1 299 740, DE 2 926 335 A1 and DE 31 32 218 A1 methods for the manufacture of throughplatings of printed circuits using conductive lacquers as well as a subsequent galvanic or currentless metallization are furthermore known.
From the German patent DE 38 06 884 C1 a method for the manufacture of throughplated printed boards on the base of a polymeric carrier material or ceramic by galvanic or currentless application of a metal layer onto the surfaces, which are not coated with a conducting metal layer, is known that is characterized in that the carrier is pre-treated in an oxidizing bath, after removal of the bath residues by rinsing the carrier is introduced into a bath which contains a monomer, in particular pyrrole or pyrrole derivates, that is electrically conducting in polymeric form, and afterwards the thus treated substrate is introduced into an acid bath, wherein an electrically conducting layer of polymerized pyrrole or pyrrole derivates is formed, whereupon bath residues are removed by rinsing, if necessary, and a galvanic metallization is carried out.
Based upon this state of the art, it is the o b j e c t of the present invention to provide an improved method for the direct metallization of non-conductive substrate surfaces, in particular polyimide surfaces.
This aim is achieved by a method for the direct metallization of non-conductive substrate surfaces, in particular polyimide surfaces, that is characterized by the process steps:
- etching the substrate surface with an acidic etching solution that contains
peroxide or peroxosulfate
- contacting the etched substrate surface with an acidic treatment solution that
contains permanganate
- activating the treated substrate surface in an acidic activation solution that
contains an oxidizing agent
- contacting the activated substrate surface with an acidic treatment solution that
contains at least a thiophen derivate and at least a sulphonic acid or a sulphonic
acid derivate and
- metallization of the thus treated substrate surface in an acidic galvanic
metallization bath.
Such method for the direct metallization of non-conducting substrate surfaces improves the state of the art in that a reliable direct metallization of non-conductive substrate
surfaces under clearly more economic and more ecologic process conditions becomes possible.
Such a process sequence in particular permits to use clearly smaller quantities of chemicals in the individual treatment solutions, which leads to a reduced environmental load.
Furthermore, in comparison to the state of the art, the process sequence according to the invention permits to work with clearly reduced treatment temperatures. Hereby, additional economic and ecologic advantages can be obtained.
In an embodiment of the method according to the invention, the etchant comprises between about 30 g/l and about 120 g/l peroxide and an acid selected from the group consisting of sulphuric acid, methane sulphonic acid, methane disulphonic acid or phosphoric acid. Advantageously, the temperature can be room temperature during the etching step, whereby supplementary heating devices and energy costs related thereto can be omitted. Suitable peroxides are for example salts of the peroxide sulphuric acid and/or the peroxisulphuric acid.
In an advantageous embodiment of the method according to the invention the etched substrate surfaces are contacted with a treatment solution containing permanganate, which comprises between about 30 g/l and 60 g/l permanganate in the form of potassium or sodium permanganate and an acid selected from the group consisting of sulphuric acid, phosphoric acid, methane sulphonic acid and methane disulphonic acid.
According to the invention, the pH value of the permanganate containing treatment solution is According to the invention, the temperature during contacting the etched substrate surfaces with the permanganate containing treatment solution can be comprised between 40 and 70°C, preferably between 50 and 60°C.
Subsequently, the substrate surfaces that have been contacted with the acid permanganate containing treatment solution are activated in an acid peroxosulphate
containing activation solution, which comprises between about 30 g/l and about 120 g/l peroxosulphate and an acid selected from the group consisting of sulphuric acid, methane sulphonic acid, methane disulphonic acid and phosphoric acid. Advantageously, the activator solution, with respect to the composition thereof, corresponds to the etching solution.
In an embodiment of the method according to the invention, the activation in the above described activation solution is carried out with ultrasonic agitation. For this, an ultrasonic generator can be introduced into an activation bath or be placed on this one.
Following the activation of the substrate surfaces to be metallized, these ones are contacted with a catalytic solution that comprises at least a thiophen derivate and at least a sulphonic acid or a sulphonic acid derivate, and that preferably comprises 3,4-ethylendioxythiophen as thiophen derivate and polystyrene sulphonic acid as sulphonic acid derivate.
The thus treated substrate surfaces can subsequently be metallized in an appropriate electrolyte for the galvanic deposition of metal layers.
Such an electrolyte can be for example an acid copper comprising electrolyte for the deposition of copper layers.
In another embodiment of the method according to the invention, the treated substrate surface can be rinsed in an acid rinsing solution, preferably in a sulphuric acid rinsing solution, before a galvanic coating with a metallic layer.
It is within the scope of the invention that rinsing steps are carried out between the individual treatment steps.
It is a special advantage of the method according to the invention that, with the exception of the step of contacting the substrate surface with an acid permanganate containing treatment solution, all process steps can be carried out at room temperature. This is in particular a reason why significant advantages can be achieved in comparison
to the methods known from the state of the art, since additional devices for setting the temperature of the process solutions can be omitted.
The treatment times of the individual process steps, with the exception of the galvanic metallization, are in a range comprised between about 1 and 3 minutes. The activation of the substrate surface that has been contacted with the acidic permanganate containing treatment solution in the acidic peroxosulphate containing activation solution can even be carried out in less than 1 minute. The same is true for the step of optionally contacting the treated substrate surface with an acidic, preferably sulphuric acid containing rinsing solution before a galvanic metallization.
The following exemplary embodiment is exemplarily representative of the method according to the invention which shall not be limited to the exemplary embodiment.
Example No. 1
A polyamide substrate having the size of 600 x 500 mm was submitted to the following treatment steps.
3 min. etching
for example 100 g/l sodium peroxidisulphate
50 g/l sulphuric acid room temperature
rinsing
3 min. conditioning
commercial conditioner
for example 40 ml/I conditioner room temperature up to 40°C
rinsing
3 min. activating in permanganate containing acid solution for example 50 g/l potassium permanganate methane sulphonic acid for setting the pH value to 2.0 +/- 0.1, 50°C
rinsing
activating the surfaces treated with permanganate for example 100 g/l sodium peroxidisulphate
50 g/l sulphuric acid
supported by ultrasonic agitation room temperature
rinsing
2-3 min. contacting the activated surfaces with a solution that contains a thiophen derivate
for example 10 ml/I of a 3,4-ethylendioxithiophen comprising solution
10 ml/I of a styrene sulphonic acid containing solution
about 2 ml/l of a phosphoric acid containing solution for setting
the pH value to 2.0 +/- 0.1 room temperature
rinsing
etching (optional)
metallization, for example Envision Cuprostar LP1
Example No. 2
A polyamide substrate having the size of 600 x 500 mm was submitted to the following treatment steps.
3 min. etching
for example 80 g/l sodium peroxidisulphate
50 g/l sulphuric acid room temperature
rinsing
3 min. conditioning
commercial conditioner,
for example 40 ml/I conditioner room temperature up to 40°C
rinsing
3 min. activating in permanganate containing acid solution for example 40 g/l potassium permanganate methane sulphonic acid for setting the pH value to 2.0 +/- 0.1
50°C
rinsing
activating the surfaces treated with permanganate
for example 80 g/l sodium persulphate (caroate)
50 g/l sulphuric acid
supported by ultrasonic agitation room temperature
rinsing
2-3 min. contacting the activated surfaces with a solution that contains a thiophen
derivate
for example 7 ml/I of a 3,4-ethylendioxithiophen comprising solution
7 ml/I of a styrene sulphonic acid containing solution
about 2 ml/l of a phosphoric acid containing solution for setting
the pH value to 2.0 +/- 0.1 room temperature
rinsing
etching (optional)
metallization, for example Envision Cuprostar LP1
Example No. 3
A polyamide substrate having the size of 600 x 500 mm was submitted to the following treatment steps.
3 min. etching
for example 80 ml/1 hydrogen peroxide (33%) 50 g/l sulphuric acid
10 ml/l of a phenolsulphonic acid containing solution
room temperature
rinsing
3 min. conditioning
commercial conditioner,
for example 40 ml/l conditioner room temperature up to 40°C
rinsing
3 min. activating in permanganate containing acid solution for example 36 g/l sodium permanganate methane sulphonic acid for setting the pH value to 2.0 +/- 0.1
50°C
rinsing
activating the surfaces treated with permanganate for example 100 g/l sodium peroxidisulphate
50 g/l sulphuric acid
supported by ultrasonic agitation room temperature
rinsing
2-3 min. contacting the activated surfaces with a solution tnat contains a thiophen derivate
for example 10 ml/l of a 3,4-ethylendioxithiophen comprising solution
10 ml/l of a styrene sulphonic acid containing solution
about 2 ml/I of a phosphoric acid containing solution for setting
the pH value to 2.0 +/- 0.1 room temperature
rinsing
etching (optional)
metallization, for example Envision Cuprostar LP1
Example No. 4
A polyamide substrate having the size of 600 x 500 mm was submitted to the following treatment steps.
3 min. etching
for example 100 g/l sodium peroxidisulphate
50 g/l sulphuric acid room temperature
rinsing
3 min. conditioning
commercial conditioner, in use in house
for example 40 ml/I conditioner room temperature up to 40°C
rinsing
3 min. activating in permanganate containing acid solution for example 50 g/l potassium permanganate methane sulphonic acid for setting the pH value to 2.0 +/- 0.1, 50°C
1 rinsirfg
activating the surfaces treated with permanganate for example 30 g/l sodium peroxidisulphate
50 g/l sulphuric acid
supported by ultrasonic agitation room temperature
rinsing
2-3 min. contacting the activated surfaces with a solution that contains a thiophen derivate
for example 10 ml/l of a 3,4-ethylendioxithiophen comprising solution
10 ml/I of a styrene sulphonic acid containing solution
about 2 ml/l of a phosphoric acid containing solution for setting
the pH value to 2.0 +/- 0.1 room temperature
rinsing
etching (optional)
metallization, for example Envision Cuprostar LP1
Example No. 5
A polyamide substrate having the size of 600 x 500 mm was submitted to the following treatment steps.
3 min. etching
for example 80 g/l sodium peroxidisulphate
50 g/l sulphuric acid room temperature
rinsing
3 min. conditioning
commercial conditioner, in use in house
for example 40 ml/l conditioner room temperature up to 40°C
rinsing
3 min. activating in permanganate containing acid solution for example 40 g/l potassium permanganate methane sulphonic acid for setting the pH value to 2.0 +/- 0.1
50°C
rinsing
activating the surfaces treated with permanganate
for example 40 g/l sodium persulphate (caroate)
50 g/l sulphuric acid
supported by ultrasonic agitation room temperature
rinsing
2-3 min. contacting the activated surfaces with a solution that contains a thiophen
derivate
for example 7 ml/l of a 3,4-ethylendioxithiophen comprising solution
7 ml/l of a styrene sulphonic acid containing solution
about 2 ml/I of a phosphoric acid containing solution for setting
the pH value to 2.0 +/- 0.1 room temperature
rinsing
etching (optional)
metallization, for example Envision Cuprostar LP1
Example No. 6
A polyamide substrate having the size of 600 x 500 mm was submitted to the following treatment steps.
3 min. etching
for example 80 ml/l hydrogen peroxide (33%) 50 g/l sulphuric acid 10 ml/l of a phenolsulphonic acid solution
room temperature
rinsing
3 min. conditioning
commercial conditioner, in use in house
for example 40 ml/l conditioner room temperature up to 40°C
rinsing
3 min. activating in permanganate containing acid solution for example 36 g/l sodium permanganate methane sulphonic acid for setting the pH value to 2.0 +/- 0.1
50°C
rinsing
activating the surfaces treated with permanganate for example 40 g/l sodium peroxidisulphate
50 g/l sulphuric acid
supported by ultrasonic agitation room temperature
rinsing
2-3 min. contacting the activated surfaces with a solution that contains a thiophen
derivate
for example 10 ml/l of a 3,4-ethylendioxithiophen comprising solution
10 ml/I of a styrene sulphonic acid containing solution
about 2 ml/l of a phosphoric acid containing solution for setting
the pH value to 2.0 +/- 0.1 room temperature
rinsing
etching (optional)
metallization, for example Envision Cuprostar LP1
Alternatively, all methods according to the invention indicated in the examples 1 through 6 were carried out with Teflon substrates that had been pre-treated with FR 4 and plasma.

We Claim:
1. A method for the direct metallization of non-conductive substrate surfaces,
in particular polyimide surfaces, characterized by the method steps:
- etching the substrate surface with an acidic etching solution that contains 30 g/l to 120 g/l peroxide
- contacting the etched substrate surface with an acidic treatment solution that contains between 40 g/l and 60 g/l permanganate
- activating the treated substrate surface in an acidic activation solution that contains between 30 g/l and 120 g/l peroxide
- contacting the activated substrate surface with an acidic catalytic solution that contains at least a thiophen derivate and at least a sulphonic acid derivate and
- metallization of the thus treated substrate surface in an acidic galvanic metallization bath.

2. A method as claimed in claim 1, wherein rinsing steps are carried out between the individual process steps.
3. A method as claimed in one of the preceding claims, wherein the etchant comprises 80 g/l to 120 g/l peroxide.
4. A method as claimed in one of the preceding claims, wherein the etchant comprises an acid selected from the group consisting of sulphuric acid and phosphoric acid.
5. A method as claimed in one or several of the preceding claims, wherein the permanganate containing treatment solution comprises an acid selected from the group consisting of hydrochloric acid, sulphuric acid, phosphoric acid, methane sulphonic acid and methane disulphonic acid.
6. A method as claimed in claim 5, wherein the treatment solution has a pH value of
7. A method as claimed in one of the preceding claims, wherein the activation solution comprises between 80 g/l and 120 g/l peroxide.
8. A method as claimed in claim 1, wherein the activation solution comprises an acid selected from the group consisting of sulphuric acid, hyrdochloric acid and phosphoric acid.
9. A method as claimed in claim 7 or 8, wherein the activation solution is identical with the etching solution with respect to the composition thereof.
10. A method as claimed in one of the preceding claims, wherein the activation is carried out with ultrasonic agitation.
11. A method as claimed in one or several of the preceding claims, wherein the thiophen derivate and sulphonic acid derivate containing treatment solution comprises at least 3,4-ethylendioxythiophen as thiophen derivate and styrene sulphonic acid as sulphonic acid derivate.
12. A method as claimed in one of the preceding claims, wherein after the treatment with the thiophen derivate and sulphonic acid derivate containing treatment solution the substrate surface is contacted with an acid, preferably sulphuric acid rinsing solution.
13. A method as claimed in one of the preceding claims, wherein the substrate surface is metallized in a copper containing metallization bath.

Documents:

190-del-2007-abstract.pdf

190-DEL-2007-Claims-(23-08-2012).pdf

190-del-2007-claims.pdf

190-DEL-2007-Correspondence Others-(23-08-2012).pdf

190-del-2007-Correspondence Others-(30-04-2012).pdf

190-DEL-2007-Correspondence-Others 1.pdf

190-del-2007-Correspondence-Others-(15-04-2011).pdf

190-DEL-2007-Correspondence-Others.pdf

190-del-2007-description (complete).pdf

190-del-2007-form-1.pdf

190-del-2007-form-18.pdf

190-del-2007-form-2.pdf

190-DEL-2007-Form-3-(23-08-2012).pdf

190-DEL-2007-Form-3.pdf

190-del-2007-form-5.pdf

190-DEL-2007-GPA-(23-08-2012).pdf

190-del-2007-gpa.pdf

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Patent Number

254775

Indian Patent Application Number

190/DEL/2007

PG Journal Number

51/2012

Publication Date

21-Dec-2012

Grant Date

17-Dec-2012

Date of Filing

31-Jan-2007

Name of Patentee

ENTHONE INC

Applicant Address

350 FRONTAGE ROAD, WEST HAVEN, CONNECTICUT 06516, USA

Inventors:

#	Inventor's Name	Inventor's Address
1	KRONENBERG, WALTER	SOLINGER STRASSE 10, 40227 SOLINGEN, GERMANY
2	HUPE, JURGEN	CARL-DIEM-WEG 14, 30764 LANGENFELD, GERMANY

PCT International Classification Number

C23C 22/00

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	06012849.3	2006-06-22	EUROPEAN UNION