METHOD AND DEVICE FOR PRODUCING METAL PATTERNS ON A SUBSTRATE FOR DECORATIVE AND/OR FUNCTIONAL PURPOSES, MANUFACTURE OF OBJECTS INCORPORATING SAID PRODUCTION AND SET OF CONSUMABLES USED

Abstract

A method for producing metal patterns, which includes depositing a temporary protection on a substrate surface corresponding to the negative of the patterns to be produced; depositing at least one metal on the areas corresponding to the patterns to be produced; and eliminating the temporary protection at least partly during and/or after, or at least partly during and/or after the deposition step. The method can produce decorative objects or functional objects such as printed circuits, integrated circuits, RFID chips, and electronic reader-readable encoding pictograms. A set of consumables used to implement the method is also disclosed.

Claims

1. Process for producing metal patterns on a substrate, comprising the following steps: A. optionally preparing the surface of the substrate intended to receive the metal patterns; B. depositing a temporary protection on the surface of the substrate corresponding to a negative of the patterns to be produced by a screen printing mask/stencil the cut-outs of which correspond to the negative of the patterns to be produced; and/or by direct printing, preferably by ink jet; C. optionally activating the surface of the substrate, in particular the areas corresponding to the patterns to be produced; D. metallization by depositing at least one metal on the areas corresponding to the patterns to be produced; E. eliminating the temporary protection of step B; F. optionally rinsing the surface of the substrate carrying the metal patterns; G. optionally drying the surface of the substrate carrying the metal patterns; H. optionally performing a finishing treatment on the surface of the substrate carrying the metal patterns; wherein step E of eliminating the temporary protection is carried out, during step D, or at least partly during step D, and/or after step D, or at least partly during and/or after the metallization step D and partly before the metallization step D.

2. Process according to claim 1, wherein step E comprises at least one of the following operations: dissolution of the temporary protection by at least one solvent utilized in the process, said temporary protection preferably being alkali-soluble so that it can be dissolved preferably by an alkaline solvent implemented in the process, entrainment in liquid phase; mechanical entrainment by a gas, preferably air.

3. Process according to claim 1, characterized wherein: the metallic deposition D is a non-electrolytic metallization by spraying of one or more redox solutions in the form of (an) aerosol(s). and wherein said process optionally comprises, before the metallization D, at least one of the following steps, preferably in the following order: I. treatment increasing the surface energy of the substrate, in the knowledge that in the event that the process comprises an activating step C, a step I of increasing the surface energy of the substrate can optionally be provided before the activation C. J. wetting the surface of the substrate; K. rinsing the surface of the substrate.

4. Process according to claim 3, wherein the metal of step D is selected from the following group of metals: silver, nickel, tin, iron, gold, cobalt, copper; oxides, alloys and combinations thereof.

5. Process according to claim 3, wherein said process includes step A, which comprises the deposition of at least one layer of varnish and/or the degreasing of the surface of the substrate intended to receive the metal patterns.

6. Process according to claim 3, wherein the treatment for increasing the surface energy of the substrate according to step I is selected from physical treatments, preferably the following physical treatments: a flame treatment, a plasma treatment and combinations thereof, and/or chemical treatments, preferably the following chemical treatments: application of a silane-based solution, depassivation of the surface using one or more acid solutions, polishing based on a rare-earth oxide, fluorination and combinations thereof.

7. Process according to claim 1, the metallic deposition D is a chemical metallization (electroless or by displacement), by immersion in one (or more) suitable metallization solution(s) and wherein said process includes activating step C and optionally, before the metallization D, at least one of the following steps, preferably in the following order: L. satin etching, preferably implemented before step C; M. rinsing the surface of the substrate in the case of satin etching according to step L.

8. Process according to claim 1, wherein the metallic deposition D is an electrolytic metallization in the case where the substrate is a conductive material per se or is treated in order to become so.

9. Process according to claim 1, wherein the finishing treatment H is the production of one or more coats of varnish and/or an electrolytic thickening composed of one or more metals.

10. Process according to claim 3, wherein a solvent allowing dissolution of the temporary protection is contained in at least one of the liquids utilized for the metallization step D and/or optionally in the liquids used in at least one rinsing step and in that the duration of this metallization step D is preferably less than or equal to the duration of dissolution of the temporary protection.

11. Process according to claim 1, wherein the metal patterns obtained are decorative and/or functional, and are preferably included in the group consisting of printed circuits, integrated circuits on a semiconductor substrate, radio frequency identification (RFID) chips, coding icons capable of being read by electronic devices, representational and/or written information identifying a product, in particular a commercial product, such as a decorative visual representation or design on a cosmetic and/or automotive product.

12. Process according to claim 1, wherein said process is implemented continuously/in-line on industrial plant.

13. Process for the manufacture of objects comprising metal patterns, preferably decorative and/or functional, wherein it includes a process according to claim 1.

14. Device for implementing the process according to claim 1, comprising: i. a module for depositing a temporary protection on the surface of the substrate; ii. a metallization module; iii. optionally a module for producing a top coat; iv. optionally a module for preparing the surface of the substrate intended to receive the metal patterns; v. optionally at least one screen printing mask/stencil useful in one of the variants of step B; vi. optionally a module for activating the surface of the substrate of step C; vii. optionally a module for eliminating, according to step E, the temporary protection of step B; viii. optionally a module for rinsing according to step F; ix. optionally a module for depositing at least one top coat according to step H.

15. Set of consumables for implementing the process according to claim 1, comprising: a. (a) consumable (s) for carrying out the temporary protection of step B; b. (a) consumable(s) for the metallization of step D; c. optionally, (a) consumable(s) for preparing the surface of the substrate intended to receive the metal patterns of step A; d. optionally at least one screen printing mask/stencil useful in one of the variants of step B; e. optionally (a) consumable(s) for activating the surface of the substrate of step C; f. optionally (a) consumable(s) for eliminating, according to step E, the temporary protection of step B; g. optionally (a) consumable(s) for rinsing according to step F; h. optionally (a) consumable(s) for depositing at least one top coat according to step H.

Description

[0181] The invention will be better understood on reading the following description of examples of the manufacture of metal patterns on different supports, with reference to the attached drawings, in which:

[0182] FIG. 1 shows a diagram illustrating the known photolithography processes for the manufacture of printed circuits.

[0183] FIG. 2 shows a diagram illustrating the protocol of Examples 1 and 2 implementing the process according to the invention with a metallization by aerosol spraying;

[0184] FIG. 3 shows the screen printing mask of Example 1;

[0185] FIG. 4 shows the metal patterns obtained in Example 1;

[0186] FIG. 5 shows the screen printing mask of Example 2;

[0187] FIG. 6 shows the metal patterns obtained in Example 2;

EXAMPLE 1

Producing Metal (Silver) Patterns on a Varnished Plastic Substrate for Decoration Purposes

[0188] -A-Surface Preparation: [0189] A UV-cross-linking varnish reference VB330R developed by the company Jet Metal Technologies is applied using a pneumatic HVLP gun with air pressure comprised between 3 and 4 bars onto an ABS (Acrylonitrile Butadiene Styrene) plate of dimensions 25 cm20 cm, degreased beforehand.
The applied plate undergoes desolvation in an oven at 60 C. for 5 minutes before polymerization in a UV enclosure (0.7 to 1.2 J/cm.sup.2 UVA).

[0190] -B-Deposition of a Temporary Protection: [0191] A film of quick-drying alkali-soluble product, Propaco SC marketed by the company SOCOMORE, containing an alkali-soluble binder, is affixed onto the varnished plate through a screen printing mask corresponding to the negative of the metallic pattern to be produced. This mask is shown in the attached FIG. 3. The lightest areas allow the alkali-soluble product/ink intended to form the temporary protection to pass through.

[0192] -I-Treatment to Increase the Surface Energy: [0193] Flame treatment via quick passes for a total duration of 5 s using a flame spray gun the flame temperature of which was adjusted to 1400 C. (After flame treatment, the substrate must have a surface energy greater than 50 dynes). [0194] After the flame treatment step, the unprotected surface must be wetting in its entirety (the spraying of water onto the surface leads to the formation of a continuous liquid film).

[0195] -C-Activating/Sensitizing: [0196] Spraying a sensitizing solution based on stannous chloride for 10 s using HVLP guns.

[0197] -K-Rinsing: [0198] Rinsing the sensitizing solution by spraying demineralized water for 10 s using an HVLP gun.

[0199] -D-Metallization/-E-Eliminating the Temporary Protection: [0200] Simultaneous spraying of an aqueous solution based on silver nitrate with a concentration of 2 g/L having an alkaline pH from 11.2+/0.2 with an aqueous solution based on glucose for 40 s using HVLP guns. [0201] The metallization takes place on the non-inked areas [0202] The ink film is evacuated on contact with the metallization solutions

[0203] -F-Rinsing: [0204] Rinsing with demineralized water for 10 s by spraying using an HVLP gun.

[0205] -G-Drying/Blowing: [0206] Drying/Blowing by alternating pulsed compressed air at 5 bars at ambient temperature

[0207] -H-Finishing [0208] The plate thus metallized is varnished by spraying using an HVLP gun and a varnish reference VM112 developed by the company Jet Metal Technologies. [0209] The plate undergoes desolvation in an oven at 60 C. for 5 minutes before polymerization in a UV enclosure (0.7 to 1.2 J/cm.sup.2 UVA).

[0210] Metallic silver patterns are thus obtained corresponding to the negative of the ink initially depositedsee FIG. 4 attached. (The non-metallized parts correspond to the areas covered by the screen printing ink).

EXAMPLE 2

Producing an Electronic Pattern on a Rigid Polymer Substrate

[0211] -B-Deposition of a Temporary Protection: [0212] A film of quick-drying alkali-soluble product, Propaco SC marketed by the company SOCOMORE, containing an alkali-soluble binder, is affixed onto an ABS plate of dimensions 25 cm20 cm through a screen printing mask corresponding to the negative of the metallic pattern to be produced. This mask is shown in the attached FIG. 5, in which the lightest areas allow the alkali-soluble product/ink intended to form the temporary protection to pass through.

[0213] -I-Treatment to Increase the Surface Energy: [0214] Flame treatment of the surface is earned out via quick passes for a total duration of 5 s using a flame spray gun the flame temperature of which was adjusted to 1400 C. (After flame treatment, the substrate must have a surface energy greater than 50 dynes). [0215] After the flame treatment step, the unprotected surface must be wetting in its entirety (spraying of water onto the surface leads to the formation of a continuous liquid film).

[0216] -C-Activating/Sensitizing: [0217] Spraying a sensitizing solution based on stannous chloride for 10 s using HVLP guns.

[0218] -K-Rinsing: [0219] Rinsing with demineralized water for 10 s by spraying using an HVLP gun.

[0220] -D-Metallization/-E-Eliminating the Temporary Protection: [0221] Simultaneous spraying of an aqueous solution based on silver nitrate with a concentration of 2 g/L having an alkaline pH from 11.5+/0.2 with an aqueous solution based on glucose for 23 s using HVLP guns. [0222] The metallization takes place on the eon-inked areas [0223] The ink film is evacuated on contact with the metallization solutions

[0224] -F-Rinsing: [0225] Rinsing with demineralized water for 10 s by spraying using an HVLP gun.

[0226] -G-Drying/Blowing: [0227] Drying by alternating pulsed compressed air at 5 bars at ambient temperature
A conductive circuit is thus obtained corresponding to the negative of the ink initially depositedsee FIG. 6 attached. (The non-metallized parts correspond to the areas coveted by the screen printing ink).
The silver deposit is sufficiently conductive to produce as electrolytic thickening With copper with a conventional copper acid bath based on copper sulphate and sulphuric acid.

EXAMPLE 3

Producing Decorative Metal Patterns In-Line by Inkjet Printing

[0228] The item made from polypropylene plastic (cylinder of 2.5 cm diameter and 8 cm high) is fixed on the conveyor upside down.

[0229] The conveyor is set in motion at a constant speed of 3 m/min and the item is rotated at 350rpm.

[0230] -A-Surface Preparation: [0231] The item is degreased by rubbing with isopropanol alcohol, then a UV-cross-linking varnish, reference VB330R containing a 3% red colorant content from the company Jet Metal Technologies is affixed, by means of 3 HVLP guns. The PP item is moved into a heat oven at 50 for a desolvatation step for 4 minutes, then enters a UV oven in which the surface of the item is irradiated with a power of 0.9 J/cm.sup.2.

[0232] -I-Treatment to Increase the Surface Energy: [0233] Flame treatment of the rotating item is earned out on the conveyor via quick passes for a total duration of 5 s using a flame spray gun the flame temperature of which was adjusted to 1400 C. (After flame treatment, the subs tune must have a surface energy greater than 50 dynes). [0234] After the flame treatment step, the unprotected surface must be wetting in its entirety (spraying of water onto the surface leads to the formation of a continuous liquid film).

[0235] -B-Deposition of a Temporary Protection: [0236] Inkjet printing by means of a Ricoh Gen4 printing head by using an alkali-sensitive TIGER ink reference Heavy Duty Ink containing an alkali-sensitive binder is carded out on the rotating item in-line (without unloading the item from the conveyor). This ink is cross-linked by UV exposure by means of a mercury bulb the power of which is 40 mJ/cm.sup.2. [0237] This printing corresponds to the negative of the desired pattern. [0238] The film-forming agent contained in the ink ensures masking of the surface; pigments are not essential for the correct operation of the process.

[0239] -C-Activating/Sensitizing: [0240] Spraying a sensitizing solution based on stannous chloride for 5 s using HVLP guns.

[0241] -K-Rinsing: [0242] Rinsing the sensitizing solution by spraying demineralized water for 10 s using an HVLP gun.

[0243] -D-Metallization [0244] Simultaneous spraying of an aqueous solution based on silver nitrate with a concentration of 2 g/L having an alkaline pH from 11.2+/0.2 with an aqueous solution based on glucose for 20 s using HVLP guns. [0245] The metallization takes place on the non-inked areas [0246] The adhesion of the alkali-sensitive ink film takes place on contact with the solutions during metallization.

[0247] -F-Rinsing/-E-Eliminating the Temporary Protection: [0248] Rinsing with demineralized water for 20 s by spraying using HVLP guns. [0249] The ink the adhesion of which was affected during the metallization step is evacuated during this rinsing.

[0250] -G-Drying: [0251] Drying by alternating pulsed compressed air at 5 bars at ambient temperature using an air blade.

[0252] -H-Finishing: [0253] The plate thus metallized is varnished by spraying using an HVLP gun and a varnish reference VM112 developed by the company Jet Metal Technologies. [0254] The plate undergoes desolvation in an oven at 60 C. for 5 minutes before polymerization in a UV enclosure (0.7 to 1.2 J/cm.sup.2 UVA).
Mirror-effect metallic silver decorative patterns are thus obtained corresponding to the negative of the ink initially deposited. The non-metallized areas allow the colour of the red base varnish to appear. Pictogram characters can be produced in order to allow the name of a trade mark or a logo to appear.

EXAMPLE 4

Producing a Silver Pattern with Electrolytic Thickening with Copper In-Line

[0255] -B-Deposition of a Temporary Protection: [0256] A quick-drying alkali-soluble ink film LINX, reference I070, is affixed by inkjet spraying (Seiko head) onto a flexible polyamide film 75 m thick placed flat on a conveyor equipped with a winder/unwinder. [0257] The inked pattern corresponds to the negative of the pattern to be produced.

[0258] -I-Treatment to Increase the Surface Energy: [0259] In order to confer an increased adhesion of the metallic deposit with the substrate, an atmospheric plasma pretreatment (rotary plasma head) was applied (after plasma treatment, the substrate must have a surface energy greater than 50 dynes). [0260] After the flame treatment step, the surface must be wetting in its entirety (spraying of water onto the surface leads to the formation of a continuous liquid film).

[0261] -C-Activating/Sensitizing: [0262] Spraying a sensitizing solution based on stannous chloride for 5 s using HVLP guns.

[0263] -K-Rinsing: [0264] Rinsing the sensitizing solution by spraying demineralized water for 10 s using an HVLP gun.

[0265] -D-Metallization/-E-Eliminating the Temporary Protection: [0266] Simultaneous spraying of an aqueous solution based on silver nitrate with a concentration of 2 g/L having an alkaline pH from 11.2+/0.2 with an aqueous solution based on glucose for 20 s using HVLP guns. [0267] The metallization takes place on the non-inked areas [0268] The ink film is solubilized and evacuated during the metallization on contact with the solutions

[0269] -F-Rinsing: [0270] Rinsing with demineralized water for 10 s by spraying using an HVLP gun.

[0271] -H-Finishing [0272] The film with silvered pattern is then guided by the conveyor to a tank containing an acid copper bath based on copper sulphate and sulphuric acid at 20 C. in order to undergo an electrolytic copper thickening of 10 m. [0273] The polyamide film is linked on one of the silvered areas to a cathode contact placed opposite the soluble copper anodes. [0274] A current density of 3A/dm.sup.2 makes it possible to produce a copper deposit of 10 m in 20 minutes.

[0275] -F-Rinsing: [0276] Demineralized water rinsing by immersion for 30 s.

[0277] -G-Drying:

[0278] Drying by alternating pulsed compressed air at 5 bars at ambient temperature

Throughout the entire process, the polyamide film is unrolled at the start of treatment, undergoes each step, then is re-rolled at the end of the process.