LT6517B - Method for selective metallization of polymeric article - Google Patents

Abstract

The present invention relates to a formation of electro-conductive areas on the surface of a polymeric article by selective metallization. The article is made from a polymer and an additive for metallization. The process consists of the selective laser activation of the areas to be metallized and subsequent deposition of said areas by a metal. The crystalline carbon particles as additives in a polymer are used. Therefore, cost-effective and high-quality circuit traces on 3D surfaces of polymeric articles can be produced by using the method with the additives of carbon particles. The size of carbon particles is from 10 nm to 1 µm and their concentration in the polymer is from 0.05 to 20 % by weight. In the activation process, a dose of laser irradiation from 0.1 to 15 J/cm² is selected in such a way that to provide structural transformation of the carbon additives into catalytic carbon clusters, which are active for the catalytic electroless plating of a metal. Metallization of the activated areas is performed by submerging the polymer article into the electroless metal plating bath.

Description

TECHNICAL FIELD

The invention relates to the formation of electrically conductive regions on the surface of a polymeric product by the selective activation of the intended metallized regions by laser irradiation followed by metal plating. The invention can be used in the manufacture of electronic and electrical devices in integrated products of complex geometric shape, molded from polymers.

TECHNICAL LEVEL

EP 1975276 (30.03.2007) discloses a selective method for metallizing a surface of a polymeric article comprising immersing said article in a first liquid, irradiating selected areas of the submerged article with laser radiation to form the areas on which the metal will be deposited. The product is further immersed in an activating liquid from which metal particles are deposited on said areas formed by laser radiation, wherein the metal particles are palladium particles and the activating liquid comprises a colloidal solution of palladium salt and tin salt. After the activation step, the article is rinsed and immersed in a chemical metallization fluid, where the metal formed by the laser-formed activated regions is coated.

The disadvantage of the known method is that laser irradiation takes place in a liquid, which makes it difficult to form electrically conductive paths on complex 3D geometric surfaces. In addition, an expensive metal palladium is used to activate the laser irradiated areas.

US2004026254 (12-02-2004) describes a selective metallization process for a dielectric material, wherein the respective dielectric material is coated with an activating layer consisting of an electrically conductive material. The activating layer is structured (evaporated) by irradiation with laser radiation to form conductive structures of the required configuration, which are then metallized. Plastic or ceramic is used as dielectric material. The coating of said activating layer is of an electrically conductive polymer which may be selected from pyrrole, furan, thiophene or derivatives thereof, as well as poly-3,4-ethylenedioxythiophene, may also be a metal sulfide or a metal polysulfide or a thin metal layer. The metallization is carried out by electroplating.

The disadvantage of the known technique is that the additional process steps required to cover the initial electrically conductive layer over the entire surface, which complicates

Selective metallization of 3D polymeric surfaces, as the layer has to be applied on a curved surface.

EP 2311048 (08-07-2009) discloses a process for selective metallization of a surface of a polymer product of a particular configuration, comprising the following sequence of operations: a) the polymer product is formed from a mixture of at least one polymeric phase and tubes containing 1-10% by weight; b) selectively heat treating the metallized areas of the polymeric surface of the product, for example by laser irradiation, thereby increasing the electrical conductivity of the irradiated areas; (c) electroplating of formed electric conductivity regions by deposition of metal ions such as copper ions.

Lack of known technique, expensive technology due to the use of expensive carbon nanotubes, this additive significantly increases the cost of the polymer product. Also, the patent only deals with galvanic metal deposition.

US2003031803 / US6743345 (2003-02-13) discloses a process for selective metallization of polymers comprising the steps of: coating an article of polymer with an active layer of a composite material consisting of another polymer into which dielectric particles of the photoreductive material are incorporated. The intended metalization of said product is irradiated with laser radiation and then immersed in an autocatalytic bath containing metal ions, deposited in a layer over the irradiated surface areas. Said dielectric particles have a size less than or equal to 0.5 micrometer. Said dielectric particles are oxides selected from ZnO, T1O2, ZrO2, Al2O3 and CeC> 2. The thickness of the composite material layer is about 1 micrometer. Said article is made of a polymeric material and said activating layer of the composite material is deposited on said article or a portion thereof by laser coating.

The disadvantage of the known method is that this method requires the application of a very thin activating layer, about 1 µm thick, which complicates the application of the method to 3D surfaces, so that the method can only be applied to the selective metallization of flat surfaces. Also, this type of metallization involves a greater number of stages, which complicates the production process.

A TECHNICAL PROBLEM IS SOLVED

The purpose of the invention is to provide an economically viable method for forming conductive paths for electronic circuits, to extend its field of application by enabling conductive paths to be formed on 3D polymeric surfaces, to accelerate the manufacturing process and to improve the quality of electrically conductive paths.

SUMMARY OF THE INVENTION According to the present invention, a method of selective surface metallization of a polymeric article, wherein the polymeric article is made of a composite material comprising a mixture of a polymer and an additive comprising laser irradiation and activation of by coating the metal regions by immersing said polymeric article in a metallization solution, the additive in said mixture of said polymeric article is crystalline carbon particles having a size of 10 nm to 1 µm and a concentration of 0.05 to 20% by weight of said mixture. laser radiation used for irradiation is pulsed or continuous laser radiation with an infrared or visible or ultraviolet wavelength and a radiation dose in the range of 0.1 to 15 J / cm ² , which is selected to alter carbon additives the crystalline structure and the irradiated areas of said article being activated so as to undergo catalytic, uncoated metal plating of the activated regions by immersion of the polymeric article after irradiation in a metalization solution containing the selected metal ions, ligand, reducing agent and buffering agent.

The crystalline carbon particles as an additive to said polymeric mixture are selected from: Furnance black: N110; N220; N330, Acetylene black, Vulcan XC 72 or Vulcan XC 72R, in the size range of 10 nm to 1 µm and in a concentration ranging from 1 to 8% by weight of said composite material.

The metal to be coated is copper, silver, nickel, cobalt, gold or platinum.

The metallization solution consists of 0,05-0,25 M copper sulphate (CuSO ₄ )); 0.15-6 M formaldehyde (CH ₂ O) as reducing agent; 0.05-0.6 M sodium carbonate (Na ₂ CO ₂ ) and 0.1-2 M sodium hydroxide (NaOH) as a buffer medium; and 0.05-0.75 M concentrations of ligands, such as hydroxycarboxylic acids (citric acid, tartaric acid, etc.) or aminopolycarboxylic acids (EDTA or DTPA or CDTA, etc.) polyhydroxyl compounds (glycerol, sucrose, etc.), poliamipolihidroksiliniai compounds (kvadrolas [CH3CH (OH) CH _2] 2NCH2CH ₂ N [CH 2 CH (OH) CH 3] 2, etc.), wherein temperature of the solution metallization being kept in the range 10 to 70 ° C and the pH value: 12 - 13 , 3.

The chemical metallization solution consists of a 0.001-0.1 M AgNC> 3 silver (l) ion source; 0,001-0,8 M CoSO ₄ - Reducer; 0.005-0.6 M sodium carbonate (Na ₂ CO 3) and 0.001-2 M sodium hydroxide (NaOH) as a buffer medium; and 0.1-1 M (NH ₄ ) ₂ SO ₄ and 0.1-5 M NH ₄ OH for Uganda, where the temperature of the solution is maintained at 30 ° C during metallization and the pH of the solution is between 12.0 and 13, 5.

Metallizing the said solution contains 0.12 M concentration of copper sulphate (CuSO ₄₎ at a concentration of 0.25 kvadrolo ([CH3CH (OH) CH 2] ₂ 2NCH2CH N [CH ₂ CH (OH) CH 3] 2, 1.25 M sodium hydroxide (NaOH), 0.3 M sodium carbonate (Na ₂ CO 3) and 1.2 M formalin (CH ₂ O), pH 12.7, 40 ° C.

The intended metallised surface areas are irradiated with pulsed laser radiation with a pulse duration in the range of 1 to 100 ns, a repetition rate in the range of 50 to 200 kHz, a wavelength in the range of 532 to 1064 nm and an irradiation dose of 1.4-3 J / cm ² , the beam transmission speed on the product surface is 1-5 m / s and the diameter of the focused gain laser beam (1 / e at intensity level ² ) on the polymeric surface is within the range of 10-200 µm, and said radiation parameters are selected to laser irradiate said product. crystalline carbon catalysts formed on the surface are suitable for chemical catalytic coating of metals in solution.

In laser-illuminated areas, catalysts are formed by cleavage but interruption of chemical bonds, crystalline carbon additives present in the polymer product.

The intended metallized surface area is irradiated with a continuous-mode CO ₂ laser of 10.6 µm and a radiation dose of 35-100 J / cm ² .

Metallization is carried out in such a way that one of the solutions suitable for chemical variation, silver plating, nickel plating, cobalting, gold plating, platinum plating is selected for metallization.

BENEFITS OF THE INVENTION

The use of crystalline carbon particles as an additive in the composite material of a polymer product allows low-cost, high-quality forming of conductive paths for electronic circuits on 3D polymeric surfaces, enabling devices that do not require separate PCBs to be integrated directly on the device body. This technology allows for a significant reduction in the size and weight of the device without the use of expensive materials to produce the device and is therefore economically viable. The price of composite material required to produce the product is only 5-20% higher than the price of the polymeric raw material, whereas analogous composites using palladium compounds or carbon nanotubes increase the price of the material by 3 to 15 times. Because the laser surface activation process in the method of the present invention has a laser irradiation threshold, the spatial resolution of metallization selectivity is improved and selected surface areas can be activated and subsequently metallized with great precision. By changing the diameter of the activating laser beam and the irradiation dose, a conductivity path width of less than 10 pm can be achieved. Due to the low dose of radiation required for activation of the pulsed nanosecond laser beam, a high laser activation rate can be achieved by rapidly scanning the laser beam in a selected contour. The effect of the laser not only exposes the carbon particles but also changes their crystalline structure to form an electrically conductive state (nanocrystalline carbon). Using pulsed radiation of 1-100 ns duration and proper selection of high pulse repetition rates, activation can be achieved at up to 5 m / s by scanning the product surface once with a laser beam. Analogous methods require high laser exposure and are therefore several or several times slower. Laser-activated polymer additives act as catalysts for the oxidation of the reducing agent (contained in the metalization solution), and the end result of the reaction is the free electrons on the surface of the laser-activated crystalline carbon. When exposed to a laser on a product surface, carbon black carbon black particles are split into smaller clusters, resulting in low electron deposits on the catalyst and creating the weak electrical potential required for the copper reduction reaction. Since copper ions are not free in solution, but exist in complexes with ligands, the yield of the reduction processes also strongly depends on the properties of the ligand. Therefore, the quadrol ligand plays a significant role here. The copper quadrol complex has a stronger adhesion (as compared to other ligands) on the catalyst surface, thus increasing the concentration of copper on small catalyst clusters. This increases the speed and quality of the metallization.

The invention is explained in more detail by the drawings which do not limit the scope of the invention and which depict:

FIG. Figure 1 is a schematic of selective metallization of a polymer, wherein

(a) the polymer is doped with crystalline carbon particles;

(b) selective surface activation by laser irradiation;

(c) metal-free immersion coating in immersion solution;

(d) an electrically conductive metal track formed in the proposed manner.

FIG. Fig. 2 shows the dependence of the resistance of the copper layer coated with the proposed method on the dose of laser radiation used for surface activation.

FIG. Figure 3 shows a coated copper strip on polypropylene with acetylene soot filler.

FIG. Figure 4 is a Raman spectrum of polypropylene with acetylene carbon black filler (a) before and (b) after laser activation. Scanned radiation parameters (0.2 W, 0.2 m / s). A wavelength of 632.8 nm is used to excite the Raman scattering. The changes in the Raman spectrum were due to changes in the crystalline state of the carbon additives caused by laser radiation.

Description of the practice of the invention

The numerals indicated in the drawings are: crystalline carbon particles - 1, polymeric product - 2, laser radiation - 3, laser impact zone for activation - 4, activated additives - 5, metallization solution - 6, metal layer - 7.

The process of the present invention has the following steps:

First stage. From the polymeric material granules and the addition of crystalline carbon particles, for example carbon black carbon black powder-granules 1, a mixture of composite material is prepared. Granules of polymeric material are mixed with carbon black carbon black powder or granules 1 by mechanical means. Carbon black carbon black - The concentration of the additive is between 0.2 and 15% by weight of said mixture. After mixing, the mixture is spray-molded to form the corresponding polymeric article 2; the crystalline carbon particles as an additive to said polymeric mixture are selected from carbon black: N110; N220; N330, acetylene soot, Vulcan XC 72 or Vulcan XC 72R.

Phase Two. Selective irradiation of the surface of the resulting polymeric article 2 with laser radiation 3 to form activated regions 4. The desired metallization site is activated by laser beam scanning a beam 3 with a galvanometric scanner. Scanning speeds can range from 0.1 to 5 m / s, depending on the material and laser parameters. The intended metallized surface areas are irradiated with pulsed laser radiation having a pulse duration in the range of 1 to 100 ns, a pulse repetition rate in the range of 50 to 500 kHz, a wavelength in the range of 532 to 1064 nm and an irradiation dose of 1.4-3 J / cm ² . Activation with pulsed nanosecond irradiation in the range of 1-100 ns activates a highly pronounced radiation dose threshold (Fig. 2), which allows for a very good spatial resolution of laser activation followed by metallization depending on the chosen radiation diameter on the surface of the product being scanned. The width of the metallized line may be narrower than 25 pm (Fig. 3). The laser-exposed sample becomes an active catalyst for the selective free-flow autocatalytic precipitation of metals from solution. Laser-exposed areas remain inactive for metallization and do not deposit metal at these sites. By acting on the surface of the sample, the laser energy absorbed locally raises the temperature of the carbon black carbon polymer and interrupts the carbon molecule bond due to thermochemical effects, resulting in numerous carbon structure clusters with active catalytic reaction edges. In other words, carbon black carbon carbon is activated, making it active for catalytic metal deposition. Not only does the carbon cluster break down due to thermochemically broken bonds, but its crystalline structure (structure) also changes. From Figure 4. The Raman spectra given can be used to observe changes in the characteristic carbon structure D and G bands after laser exposure. After activation, three major changes occur: narrowing of the D and G bands, increasing their relative intensity (D / G), and shifting the G band to the shorter wave region. All these changes indicate the reduction of structural defects in the crystalline state, the formation of clusters, and the appearance of boundary defects, which determine the catalytic activity of these derivatives.

Stage Three. Immersion of the selectively irradiated polymeric layer in a metalization solution 5 containing selected metal ions, Uganda, a reducing agent and a buffer material, which undergoes autocatalytic metal plating of the activated regions from the solution. For the autocatalytic coating of metals, various metal solutions can be used: copper, nickel, palladium, silver, cobalt, gold or platinum. The composition of the variation solution can be selected from: 0.05-0.25 M copper sulphate (CuSO ₄ ); 0.15-6 M formaldehyde (CH ₂ O) as reducing agent; 0.05-0.6 M sodium carbonate (Na ₂ CO ₃ ) and 0.1-2 M sodium hydroxide (NaOH) as buffer; and 0.05-0.75 M concentrations of ligands, such as hydroxycarboxylic acids (citric acid, tartaric acid, etc.) or aminopolycarboxylic acids (EDTA or DTPA or CDTA, etc.) polyhydroxyl compounds (glycerol, sucrose, etc.), polyamipolihydroxyl compounds (square [CH ₃ CH (OH) CH ₂ ] ₂ NCH ₂ CH ₂ N [CH ₂ CH (OH) CH ₃ ] ₂ , etc.) wherein the temperature of the solution is maintained at 10 to 70 ° C during the metallization, and the pH of the solution is 12 to 13.3. The composition of the silver plating solution can be selected from: 0.001 to 0.1 M AgNO ₃ -Silver (I) ion source; 0.001 - 0.8 M CoS0 ₄ - Reducer; 0.005-0.6 M sodium carbonate (Na ₂ CO ₃ ) and 0.001-2 M sodium hydroxide (NaOH) as buffer medium; and 0.1-1 M (NH ₄ ) ₂ SO ₄ and 0.1-5 M NH ₄ OH - ligands, where the temperature of the solution is maintained at 30 ° C during the metallization and the pH of the solution is from 12.0 to 13 , 5. A copper solution was used for copper plating consisting of 0.12 M copper sulphate (CuSO ₄ ), 0.25 M quadrole ([CH ₃ CH (OH) CH ₂ ] ₂ NCH ₂ CH ₂ N [CH ₂ CH (OH) ) CH ₃ ] ₂ ), a mixture of 1,25 M sodium hydroxide (NaOH), 0,3 M sodium carbonate (Na ₂ CO ₃ ) and 1,2 M formalin (CH ₂ O), pH = 12, 7, temperature 40 ° C. Variation bath temperature 10-70 ° C.

The anionic formaldehyde oxidation reaction, the product of which is free electrons on the surface of the catalyst, is carried out at the beginning of the flowless autocatalytic coating. Further in the autocatalytic process, the cathodic reduction of copper by electrons on the catalyst surface takes place. Since copper ions are not free in solution, but exist in complexed ligand compounds, the yield of the reduction processes strongly depends on the properties of the ligand: both its strength to the metal ion and the adsorption of the compound on the catalyst surface. When a propellant solution is used for metallization, the electron deposits on the catalyst surface formed during the anodic oxidation reaction of the reducer act as an electrical potential for the copper reduction reaction. Since the metal ions in the solution are not free but exist in complexes with the ligands, the yield of the reduction processes is also strongly dependent on the properties of the ligand: both its strength to the metal ion and the adsorption of the compound on the catalyst surface. The electrons formed during the anodic oxidation reaction of the reducing agent give the catalyst surface a negative charge favoring the reduction of the metal ions. In the case of variation, the quadrol ligand plays a significant role. The copper (II) quadrol complex has a stronger adhesion (as compared to other ligands) to the catalyst surface, thus increasing the concentration of copper on the catalyst clusters. This increases the speed and quality of the metallization. After the metallization step, a metal layer 6 is integrated into the polymeric article on the surface of the polymeric article.

Example 1

Material: In this example, the composite material was prepared from polypropylene (PP Hostacom CR 1171 G1) beads and acetylene carbon black powder containing 1 to 5 percent. by mass, which are mixed at high temperature. The mixing tank is maintained at 170-180 ° C. Mixing time is 4-5 minutes. The material is then sprayed into the mold. The temperature of the sprayed composite was 175-195 ° C and the pressure of the sprayed material was 20 bar.

Laser Activation: Selective laser activation of the surface utilizes the fundamental harmonic (wavelength: 1064 nm) of a pulsed nanosecond Nd: YAG laser (Baltic HP, EKSPLA). The pulse repetition rate is selected in the range 50-100 kHz. Laser beam broadcasting was performed with a galvanometric scanner (SCANLAB) and an 80mm focal length f-theta telecentric lens was used for focusing. The diameter of the scanned Gaussian beam on the sample surface (at intensity level 1 / e ² ) was 85 µm. In this example, tracks with a width ranging from single line to multiple lines with overlap of 40 pm lines were activated. The scan speed, at a pulse repetition frequency of 50 kHz, was 1 m / s; and at a pulse repetition rate of 100 kHz to 2 m / s.

Metal Deposition: After laser activation, the specimens were immersed in a spinning solution consisting of: 0.12 M CuSO ₄ (copper sulfate) 0.35 M KNaC4H4O ₆ -4H ₂ O (sodium potassium tartrate) 1.25 M NaOH (caustic soda) , 0.3 M

Na 2 CO 3 (sodium carbonate), 1.2 M CH 2 O (formalin), pH = 12.7. Coating was carried out for 60 min at 40 ° C.

Results: Following copper deposition processes, microscopic analysis of copper-plated lines was performed to show that the narrowest line width (scanning lines without overlap) was 19.6 pm. The surface impedance was also measured using the Keithley 2002 multifunctional gauge. The surface impedance was <R _S > = 3Ί0 ′ ³ Ω / π. To measure adhesion, an adhesive tape test was performed, after which all the coated metal layer remained on the surface of the article.

Example 2

Material: In this example, the composite material was prepared from polycarbonate and acrylonitrile butadiene styrene (PC / ABS Bayblenb T65) beads and acetylene carbon black (specify particle size limits) powder (1 to 5% by weight) mixed at high temperature with said beads. . The mixing vessel is maintained at a temperature of 270-280 ° C. Mixing time is 4-5 minutes. The material is then sprayed into the mold. The temperature of the sprayed composite was 280-290 ° C and the pressure of the sprayed material was 20 bar.

Laser Activation: For selective laser surface activation uses second-harmonic (wavelength: 532 nm) pulse nanosecond Nd: YAG laser (Baltic HP, EKSPLA) pulse repetition frequency 50 kHz. The laser beam is broadcast using a galvanometric scanner (SCANLAB) and is focused by an 80mm F-Theta telecentric focal length lens. The diameter of the scavenging Gaussian beam on the sample surface (at intensity level 1 / e ² ) was 95 µm. In this example, tracks with a width ranging from single line to multiple lines with overlap of 40 pm lines were scanned. The scanning speed at 50 kHz was 1 m / s.

Metal Deposition: After activation of the laser samples were immersed in the electroless copper plating solution consisting of: 0.12 M CuSO 4 (copper sulfate) 0.35 ₄ M KNaC4H O6-4H ₂ O (sodium potassium tartrate), 1.25 M NaOH (sodium alkaline), 0.3 M Na ₂ CO ₃ (sodium carbonate), 3.4 M CH 2 O (formalin), pH 12.7. Coating was carried out for 60 min at 30 ° C.

Results: Coating lines were followed by microscopic analysis of the coated lines, which showed that the narrowest line width (scanning lines without overlap) was 20.1 pm. The surface impedance was also measured using a Keithley 2002 multifunctional gauge. The surface impedance was <R _S > = 8Ί0 ′ ³ Ω / π. To measure adhesion, an adhesive tape test was performed, after which all the coated metal layer remained on the surface of the article.

Claims (10)

DEFINITION OF INVENTION A process for the selective metallization of a surface of a polymeric article, wherein the polymeric article is made of a composite material consisting of a mixture of a polymer and an additive comprising the following sequence of operations: laser irradiation of the metallised surface areas of the polymeric product by activating these areas, coating the activated regions with a metal by immersing said polymeric product in a metallization solution, characterized in that the additive in said polymeric product in said mixture is crystalline carbon particles having a size of 10 nm to 1 pm and at a concentration of 0.05% to 20% by weight of said mixture, the laser radiation used for irradiation is pulsed or continuous laser radiation with a wavelength of infrared or visible or ultraviolet radiation and a radiation dose of 0, 1 to 15 J / cm ² , which is selected to alter the crystalline structure of the carbon additives and to activate the irradiated areas of said article so as to undergo catalytic uncoated metal plating by immersing the polymeric article after irradiation in a metalization solution of s contains metal ions, ligand, reducing agent and buffering agent selected for coating. 2. The metallization process of claim 1, wherein the crystalline carbon particles as an additive to said polymeric mixture are selected from: Furnance black: N110; N220; N330, Acetylene black, Vulcan XC 72 or Vulcan XC 72R, in the size range of 10 nm to 1 µm and in a concentration ranging from 1 to 8% by weight of said composite material. 3. The method of metallization according to any one of the preceding claims, characterized in that the metal to be coated is copper, silver, nickel, cobalt, gold or platinum. 4. The metallization process according to any one of the preceding claims, characterized in that the metallization solution comprises copper sulphate (CuSO ₄ ) at a concentration of 0.05-0.25 M; 0.15-6 M formaldehyde (CH2O) as reducing agent; 0.05-0.6 M sodium carbonate (Na ₂ CO ₃ ) and 0.1-2 M sodium hydroxide (NaOH) as buffering medium; and 0.05-0.75 M concentrations of ligands such as hydroxycarboxylic acids (citric acid, tartaric acid, etc.) or aminopolycarboxylic acids (EDTA, or DTPA, or CDTA, etc.) polyhydroxyl compounds (glycerol, sucrose, etc.), polyamipolyhydroxylic compounds (quadrol [CH ₃ CH (OH) CH 2] 2NCH ₂ CH ₂ N [CH ₂ CH (OH) CH 3] ₂ , etc.) wherein the temperature of the solution is maintained between 10 and 70 ° C during the metallization and the pH of the solution is between 12 and 13.3 . 5. A process according to claim 1, wherein the chemical metallization solution comprises a 0.001-0.1 M AgNO ₃ - silver (I) ion source; 0.001-0.8 M COSO4 - Reducer; 0.005-0.6 M sodium carbonate (Na ₂ CO ₃ ) and 0.001-2 M sodium hydroxide (NaOH) as a buffer medium; and 0.1-1 M (NH 4 SO 2 and 0.1-5 M NH 4 OH ligands, where the solution temperature is maintained at 30 ° C during the metallization and the solution has a pH of 12.0 to 13.5. 6. The metallization process of claim 4, wherein said metallization solution comprises 0.12 M copper sulfate (CuSO ₄ ), 0.25 M quadrole ([CH ₃ CH (OH) CH ₂ ] ₂ NCH ₂ CH ₂ N [CH ₂ CH (OH) CH ₃ ] 2), 1.25 M sodium hydroxide (NaOH), 0.3 M sodium carbonate (Na ₂ CO ₃ ) and 1.2 M formalin (CH ₂ O), pH = 12.7, temperature 40 ° C. 7. The method of metallization according to any one of the preceding claims, characterized in that the intended metallised surface areas are irradiated with pulsed laser radiation having a pulse duration in the range of 1 to 100 ns, a repetition rate in the range of 50 to 200 kHz and a wavelength in the range 532 to 1064 nm, radiation dose 1.4-3 J / cm ² , beam speed on product surface 1-5 m / s, and focused Gaussian laser beam diameter (at 1 / e ² intensity level) on polymeric surface is within 10 -200 pm, and said radiation parameters are selected such that the crystalline carbon catalysts formed in the laser-irradiated surface of said article are suitable for chemical catalytic coating of metals in solution. 8. The method of metallization according to claims 1, 2 and 7, characterized in that the radiation dose is chosen such that the catalysts are formed in the laser-illuminated areas by cleavage but without interruption of the chemical bonds, crystalline carbon additives present in the polymer product. 9. The method of metallization according to any one of the preceding claims, characterized in that the surface area to be metallized is irradiated with a continuous-mode CO2 laser at a wavelength of 10.6 µm and an irradiation dose of 35-100 J / cm ² . The metallization process according to any one of the preceding claims, characterized in that one of the solutions suitable for chemical variation, silver plating, nickel plating, cobalting, gold plating, platinum plating is selected for metallization.